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[415 After
performing
an
in-plane
R
average of, e.g., the potential V (z ) = 1=S S V (x; y; z )dxdy (S is the in-plane area
of the surfa e unit ell) an additional \running" average over the extension of a unit
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lines O(N ) ode was originally implemented for s and p fun tions only (D. Drabold,
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[335 This algorithm has been developed by W. G. Aulbur in ollaboration with L. Steinbe k,
M. M. Rieger, and R. W. Godby.
[336 For GaAs, we in lude unpublished data provided by F. Aryasetiawan [290. For Ge,
GaAs, and SiC we in lude unpublished 60 Gaussian orbital data by Rohl ng, Kruger,
and Pollmann [303.
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213

[306 All real-spa e/imaginary-time algorithms implemented so far are based on pseudopotentials and use plane waves as basis fun tions.
[307 The index i has been repla ed by the band index n and the re ipro al ve tor k in the
rst Brillouin zone. Spin is disregarded. The Fermi energy lies in the band gap, i.e.,
uno
"o
nk < 0 and "nk > 0.
[308 The r and r0 meshes are not o set whi h onsequently requires spe ial treatment of
the Coulomb divergen y, see Ref. [103.
[309 Assume a spheri al intera tion ell for simpli ity.
[310 Materials su h as GaN with larger density variations than Si will require an even
smaller r to obtain similar onvergen e. The range of the intera tion ell should
not in rease although the diele tri onstant of GaN is less than half of the diele tri
onstant of Si sin e the short-range Green fun tion determines the range, not the
long-range s reened intera tion.
[311 L. Steinbe k, private ommuni ation. Note that Steinbe k, Rieger, and Godby re ently
developed algorithms that redu e memory requirements by an order of magnitude.
[312 We dis uss the ase of an RPA-based GWA al ulation for simpli ity.
[313 This so- alled \mixed-spa e" representation of the non-lo al operators in the GWA
was introdu ed by Godby et al. [185 and dis ussed in detail by Blase et al. [279.
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Brillouin zone boundary.
[317 The ase of C (E ) is analogous and will not be dis ussed here.
[318 W. H. Ba kes, private ommuni ation.
[319 B. Wenzien, G. Cappellini, and F. Be hstedt, Phys. Rev. B 51, 14701 (1995).
[320 Similar on lusions hold for the onvergen e properties of the plasmon-pole parameters,
point (v ), whi h are not presented here.
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Engineers (M Graw-Hill, New York, 1978), p. 369.
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dis ussion thereof).
212

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[293 M. Alouani and J. Wills, as presented in Ref. [542.
[294 In ontrast to most other GWA al ulations, Kubo also uses a linear tetrahedron
method for the evaluation of Brillouin zone integrals.
[295 M. Rohl ng, diploma thesis, University of Munster, Germany, unpublished.
[296 The LDA band stru ture of Ref. [42 is al ulated at 10 spe ial k-points and a 10
Hartree ut-o . Comparison with a al ulation using 60 spe ial k-points and an energy
ut-o of 18 Hartree leads to shifts in the eight lowest eigenvalues at , X , and L by
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[299 as in Ref. [182, Vol. 17 b.
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respe tively.
[305 The energy ut-o used for the ore ase is 6.75 Hartree and 9.5 Hartree for the valen e
ase. Negle t of s alar relativisti e e ts in reases the gap by about 0.3 eV to 1.93 eV
( ore) and 0.67 eV (valen e) [301.
211

[268 For a riti al dis ussion of Mahan's photoemission theory for the determination of the
alkali metal photoemission spe tra, see, for instan e, Ref. [11.
[269 The lo al- eld fa tor f (q ) is obtained by tting the diele tri onstant to quantum
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polarizability and the GWA self-energy for a 1D semi ondu ting wire. We will not
dis uss that model system but on entrate on the results for Si.
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210

[246 M. M. Rieger and R. W. Godby, Phys. Rev. B 58, 1343 (1998).


[247 All quantities are to be interpreted as matri es with respe t to plane-wave oe ients
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[248 Spe ial are must be taken to a ount for ore harges that are missing in the pseudopotential approa h of Ref. [246.
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209

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208

[206 M. Born and W. Heisenberg, Z. Phys. 23, 388 (1924).


[207 Cal ulations of in the time-dependent Hartree-Fo k approximation, i.e., in luding
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[209 As ited in Ref. [43.
[210 Note, that the orre t ordering of the lowest ondu tion bands in Ge an also be
a hieved in al ulations that have no self-intera tion errors [211, 212. The energies of
the lowest-lying ondu tion bands in these methods deviate signi antly from experiment (ECB at L
X = 0.10 eV - 0.12 eV - 0.53 eV (Ref. [211), 1.01 eV - 1.28
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[165 To be onsistent with Hanke et al.'s notation we do not onsider density u tuation
operators n^ 0 (rt) = n^ (rt) hn^ (rt)i as in Eqs. (28) and (29) but density operators n^ (rt).
For the de nition of the physi ally relevant retarded diele tri matrix both approa hes
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^ r1 t1 ) (
^ r2 t2 )
^ y (r4t4 )
^ y(r3 t3 )jN; 0i:
G(r1 t1 ; r2 t2 ; r3 t3 ; r4 t4 ) = ( i)2 hN; 0jT [ (
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[144 Hybertsen and Louie use a plasmon-pole model, Godby and ollaborators determine
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[78 S reening e e ts due to inhomogeneous density distributions are in this arti le simply
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[59 See Se tions 7, 11, and 30 for further dis ussions of this point.
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[61 We add in nitesimal onvergen e fa tors i to Ei for Ei <> .
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hole in a solid via a photoemission pro ess. The ele tron loud will ontra t around
the ore hole to s reen it, whi h leads to ex itation or ionization of the residual ion {
the so- alled shake-up and shake-o pro esses.
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200

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[41 For a more detailed des ription see Appendix A.
[42 W. G. Aulbur and J. W. Wilkins, unpublished.
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[48 X. Zhu and S. G. Louie, Phys. Rev. B 43, 14142 (1991).
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[50 S. Massidda, R. Resta, M. Posternak, and A. Balderes hi, Phys. Rev. B
(1995).

52,

R16977

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10780 (1994).

50,

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55,

[55 F. Aryasetiawan and O. Gunnarsson, Phys. Rev. Lett. 74, 3221 (1995).
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on the Physi s of Semi ondu tors, Van ouver, BC, Canada, edited by D. J. Lo kwood
(World S ienti , Singapore, 1995), Vol. 1, p. 161.
199

[18 A. L. Fetter and J. D. Wale ka, Quantum theory of many-parti le systems (M GrawHill, New York, 1971).
[19 P. Fulde, Ele tron Correlations in Mole ules and Solids, Springer Series in Solid-State
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[20 J. C. Inkson, Many-body theory of solids (Plenum Press, New York, 1984).
[21 G. D. Mahan, Many-Parti le Physi s (Plenum Press, New York, 1993), 2nd edition.
[22 R. D. Mattu k, A Guide to Feynman Diagrams in the Many-Body Problem (Dover,
New York, 1992).
^ rt) destroys an ele tron at point r and time t.
[23 (
[24 Quasiparti le life times in Si are dis ussed in onne tion with Fig. 15.
[25 Typi al values of Z for semi ondu tors are listed in Table 9.
[26 L. Hedin, Nu l. Instr. Meth. Phys. Res. A308, 169 (1991).
[27 L. Hedin, Int. J. Quant. Chem. 56, 445 (1995).
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[30 N. V. Smith, P. Thiry, and Y. Petro , Phys. Rev. B 47, 15476 (1993).
[31 Other independent-parti le Hamiltonians su h as Hartree, Hartree-Fo k, or empiri al
pseudopotential Hamiltonians have been used as well but to a mu h lesser extent. See,
for instan e, Se tions 7 and 9.
[32 P. Hohenberg and W. Kohn, Phys. Rev. 136, B864 (1964).
[33 W. Kohn and L. J. Sham, Phys. Rev. 140, A1133 (1965).
[34 See Appendix A for a brief review of Kohn-Sham theory and other important on epts
of density fun tional theory.
[35 For a formal expression of the ex hange- orrelation potential, see, for instan e,
L. J. Sham, Phys. Rev. B 32, 3876 (1985), and referen es therein.
[36 In a rystalline system, i stands for the ombination of a band index n, a spin index
s, and a wave ve tor k.
[37 R. O. Jones and O. Gunnarsson, Rev. Mod. Phys. 61, 689 (1989).
198

Referen es
[1 We use atomi units throughout this arti le unless otherwise noted. In these units,
energy is measured in Hartree and h = e = me = 4"0 = 1, "0 is the permittivity of
va uum.
[2 The self-energy  is related to G via Dyson's equation, see Chapter II, Eq. (16).
[3 L. Hedin, Phys. Rev. 139, A796 (1965).
[4 L. Hedin and S. Lundqvist, in Solid State Physi s, Vol. 23, edited by F. Seitz, D. Turnbull, and H. Ehrenrei h (A ademi , New York, 1969), p. 1.
[5 M. S. Hybertsen and S. G. Louie, Phys. Rev. Lett. 55, 1418 (1985).
[6 R. W. Godby, M. S hluter, and L. J. Sham, Phys. Rev. Lett. 56, 2415 (1986).
[7 M. S. Hybertsen and S. G. Louie, Comments Cond. Mat. Phys. 13, 223 (1987).
[8 F. Be hstedt, in Festkorperprobleme/Advan es in Solid State Physi s
U. Rossler (Vieweg, Brauns hweig/Wiesbaden, 1992), p. 161.

32,

[9 R. W. Godby, in Uno upied ele troni states, Topi s in Applied Physi s


J. E. Ingles eld and J. Fuggle (Springer, New York, 1992).

ed. by
69,

ed.

[10 G. D. Mahan, Comm. Cond. Matt. Phys. 16, 333 (1994).


[11 G. D. Mahan and E. W. Plummer, to appear in Handbook of Surfa es, Vol. 2, edited
by K. Horn and M. S heer.
[12 J. Pollmann, P. Kruger, M. Rohl ng, M. Sabis h, and D. Vogel, Appl. Surf. S i. 104105, 1 (1996).
[13 B. Farid, to be published in Ele tron orrelation in the solid state, edited by
N. H. Mar h (World S ienti /Imperial College Press).
[14 F. Aryasetiawan and O. Gunnarsson, Rep. Prog. Phys. 61, 237 (1998).
[15 We all basis sets that ontain fun tions whi h are expli itly entered at atomi sites
(e.g., LMTO, Gaussian orbitals, et .) lo al-orbital basis sets in this arti le.
[16 The self-energy equals the energy of the bare parti le intera ting with itself via the
polarization loud that the parti le generates in the many-body system.
[17 A. A. Abrikosov, L. P. Gorkov, and I. E. Dzyaloshinski, Methods of Quantum Field
Theory in Statisti al Physi s (Dover, New York, 1975).
197

Figure 50: The parameter de ned by Ex = P and approximated by = 1=LDA 1=expt


for 11 semi ondu tors and insulators (from Ref. [592). The solid line is a linear t to the
data. The broken urves show how mu h varies when LDA is hanged by 5%. For
small- and medium-gap materials with a bond length above 5 bohr, the value for is almost
material independent. For larger gap materials, be omes gradually lower in absolute value
as the bond length de reases.

196

Figure 49: E e ts of quasiparti le weights and vertex orre tions on the imaginary part
of the diele tri onstants for diamond and sili on (from Ref. [564): short dashed line {
experiment (diamond Ref. [197, Si Ref. [565); dotted line { LDA; long-dashed line { selfenergy orre ted without quasiparti le-weight orre tion; dash-dotted { self-energy orre ted
with weight fa tor Z Zv for ea h matrix element; solid line { self-energy orre ted in luding
vertex orre tions. The lose agreement between the solid and long-dashed urve shows that
the strong e e t of the weight fa tor Z Zv is almost an eled by vertex orre tions. Sin e
the dotted LDA urves look almost like solid lines, note that the LDA urves are farthest to
the left and have the highest peak in both materials.

195

Figure 48: Imaginary part "2 (! ) of diele tri fun tions for GaAs and GaP from Ref. [556.
The solid urve was obtained with a FLAPW (full-potential linearized augmented plane
wave) band stru ture with a s issors shift hosen to t the experimental band gap. This
hoi e of s issors shift puts the dominant peaks in the absorption spe tra about 0.5 eV too
high ompared to experiment (dashed lines { GaAs Ref. [197; GaP Ref. [274).

194

40
Ge

30
Se

100(LDA - expt)/expt

GaAs

20
Si

AlAs
GaP
AlP

10

quartz
SiC

GaN
0

AlN

5
10
direct band gap (eV)

BN

15

Figure 47: Per ent deviation of the LDA diele tri onstants from experiment for 13
semi ondu tors and insulators. The numeri al and experimental data are from Refs.
[536, 540, 541, 542, 543. The al ulations use s alar relativisti pseudopotentials.

193

0.00

Energy (a.u.)

0.10

0.20

LDA
GW
Image

0.30

0.40
10.0

5.0
0.0
5.0
10.0
Distance outside surface (a.u.)

15.0

Figure 45: Surfa e averaged e e tive lo al potential (Eq. (130)) at the Al(111) surfa e
ompared with the exponentially de aying LDA ex hange orrelation potential Vx LDA . The
lo al potential al ulated from the GWA self-energy (i) is virtually identi al to Vx LDA in the
Al-region, and (ii) rosses over to the lassi al image form (best t shown) in the va uum
in ontrast to Vx LDA . Figure taken from Ref. [499.
4.00
LDA
GW

|QP|

3.00

2.00

1.00

0.00
5.0

0.0
5.0
10.0
15.0
Distance outside surface (a.u.)

Figure 46: Surfa e-state quasiparti le wave fun tion (full line) of the Al(111) surfa e at
1.66 eV below the va uum level in omparison to its LDA ounterpart (dashed line). Sin e
the lo al potential resulting from the self-energy de ays as 1=z , z being the distan e from
the surfa e, rather than exponentially as does the LDA ex hange- orrelation potential, the
quasiparti le state has weight transferred into the va uum relative to the LDA state. The
quasiparti le state is obtained by an iterative solution of the energy-dependent quasiparti le
equation. Figure taken from Ref. [499.
192

Figure 44: The absolute value of the quasiparti le energies of the highest-o upied (left)
and lowest-uno upied (right) states in potassium as a fun tion of luster size in LDA (open
ir les), GWA ( lled ir les), and experiment (triangles, data from Refs. [517, 518, 519, 520,
521). The rosses represent LDA total-energy di eren es (SCF) between positive (K+n ) and
neutral (left hand side) lusters or between neutral (Kn ) and negative (Kn , right hand side)
lusters. The LDA al ulation is not possible for small (n = 2 and 8) lusters. GWA tra ks
experiment and the SCF al ulations losely for the highest-o upied states in ontrast to
LDA. The same is true for the lowest-uno upied state although the improvement over LDA
is less dramati . Figure adapted from Ref. [523.

191

Figure 43: Photoemission peak positions as a fun tion of photon energy for the Na (110)
surfa e. The quasiparti le (QP) bands in lude the real and imaginary part of the self-energy
and are represented by solid urves. The QP bands are narrower than the nearly-free-ele tron
bands (NFE, dashed urves) by 0.37 eV. The full theory (solid dots) also in ludes surfa e
e e ts and reprodu es the sharp peaks in the \gap" at photon energies of about 35 eV.
Experimental data are denoted by rosses and taken from Ref. [505. Figure taken from
Ref. [229.

190

Figure 42: Self-energy of a 5s photoele tron in Ag relative to the Fermi energy as a fun tion of
energy. The di erent urves are for (i) the bare ex hange due to the 5s ondu tion ele trons
(dotted line), (ii) the s reened ex hange due to the 5s ondu tion ele trons (dashed line),
(iii) the s reened ex hange due to the 5s ondu tion ele trons and in luding the e e ts
of a nite imaginary part of the self-energy (dash-dotted line), (iv ) same as in (iii) but
adding the bare ex hange with the ore ele trons (solid line a), and (v ) same as in (iii) but
adding the s reened ex hange with the ore ele trons (solid line b). Experimental data from
Ref. [500 are given as squares. In lusion of ex hange with the ore ele trons hanges the
energy dependen e of the self-energy qualitatively. S reening and a non-zero imaginary part
of the self-energy a e t the results quantitatively. Figure taken from Ref. [216.

189

Figure 41: Self-energy ontribution to the energy of the Ag 5s photoele tron arising from the
ex hange intera tion with ele trons in the lled valen e shell (n = 4) for di erent values of the
angular momentum l (dashed lines). Comparison of the sum of the s, p, and d ontributions
(dashed-dotted line) with the solution that takes the e e t of dynami s reening into a ount
(solid line) shows that ex hange is dominant. Energies are measured from the Fermi level.
Figure taken from Ref. [216.

188

s-d promotion energy (eV)

HF
GWA
Exp.
LSD
LSDSX

-3

Ca

Sc

Ti

V
Cr Mn Fe Co
Element of iron series

Ni

Cu

Figure 40: The neutral s ! d promotion energies (eV) for the iron series elements from
experiment, Hartree-Fo k (HF), and GWA (Ref. [67) and from the lo al spin density approximation (LSDA) and from the s reened-ex hange lo al spin density approximation (LSDSX) [486 from Ref. [485. GWA improves upon Hartree-Fo k for all elements and upon
the lo al spin-density approximation for the rst half of the series but annot ompete in
a ura y with the s reened ex hange lo al spin density results. The gure ombines data
from Refs. [67 and [485.

187

Figure 39: The imaginary part of the diele tri fun tion "2 (! ) = Im["(! ) as a fun tion
of h ! for Si (upper panel, adapted from Ref. [474) and diamond (lower panel, adapted
from Ref. [475). For Si, the dots orrespond to experiment [274, the solid line in ludes
lo al elds and ele tron-hole attra tion in the Hamiltonian, the long-dashed line in ludes
only lo al elds, and the short-dashed line only RPA s reening with quasiparti le shifts.
The low-energy experimental peak is ommonly referred to as the E1 peak, and the highenergy experimental peak is referred to as the E2 peak. For diamond, the left panel ontains
theoreti al results negle ting the ele tron-hole intera tion (dashed lines), and experimental
results from Ref. [142, 478 (solid lines). The right panel ontains theoreti al results in luding
the ele tron-hole intera tion (dashed line) and the same experimental results (solid line).
Ex itoni e e ts improve agreement between theory and experiment signi antly for peak
position and height and are larger in large-gap materials su h as diamond than in mediumgap semi ondu tors su h as Si.
186

Figure 38: Minimum band gap of orientationally ordered solid mole ular hydrogen in the h p
stru ture as a fun tion of density and hen e pressure for Hartree-Fo k (HF), GWA (GW),
and LDA. GWA is lose to Hartree-Fo k for low densities and lose to LDA for high densities.
Lines are drawn as a guide to the eye. Figure taken from Ref. [457.

185

Figure 37: Quasiparti le band stru ture of the C(111) (21) surfa e for slightly bu kled,
undimerized  -bonded hains (left panel) [443 and dimerized but unbu kled  -bonded hains
(right panel) [444. Only geometry (b) leads to semi ondu ting rather than metalli behavior
and a surfa e gap of 1.7 eV [445 in good agreement with the experimental gap of about 2.0
eV [447. The proje ted bulk quasiparti le band stru ture is shown in bla k. Figure adapted
from Ref. [445.

184

Figure 36: GWA (solid line), LDA (dashed line), and experimental photoemission data
(diamonds: Refs. [438, 439, 440; ir les: Refs. [441, 442) for o upied and uno upied
states of the lean Ge(001) (21) surfa e. Clear dis repan ies with experiment exist for the
dispersion of the uno upied Ddown state, the o upied Dup state between JK/2 and J0 , and
for the dispersion of the o upied states at . The proje ted bulk GWA band stru ture
is shadowed and energies are measured with respe t to the valen e band maximum. Open
symbols represent weak features in the experimental spe tra. Figure taken from Ref. [437.

183

Figure 35: Left panel: LDA and quasiparti le (QP) Ge(111):As (11) surfa e-state energies in omparison to the proje ted bulk quasiparti le band stru ture (shaded) along highsymmetry dire tions in the surfa e Brillouin zone. Quasiparti le orre tions (i) open up the
gap between the surfa e states, (ii) eliminate the unphysi al, at LDA dispersion at  , and
(iii) improve the position of the o upied surfa e bands with respe t to the valen e band
maximum in omparison to experiment. Right panel: Cal ulated o upied quasiparti le surfa e state energies ompared to angle-resolved photoemission data (Ref. [433). Agreement
between theory and experiment is within the quoted theoreti al un ertainty of 0.1 eV.
Figure adapted from Ref. [432.

182

E c,A

Ec
E c,B
E gap,A

E gap,B
E v,B

E v,A

Ev
V(z)
<VH >B

n(z)
-Vdipole
<VH >A

E gap = E v+ E c

E v = Ev,A- E v,B+ Vdipole

Figure 34: S hemati representation of the volume-averaged dipole density n(z ) (dashed
line), the Hartree potential V (z ) (solid line), and the interfa e ondu tion-band o set, E ,
and valen e-band o set, Ev , of two semi ondu tors A and B. In the semi ondu tor bulk
regions, V (z ) equals the average Hartree potential hVH iA(B) whi h serves as an energy referen e for the bulk valen e band maximum (Ev;A(B) ) and bulk ondu tion band minimum
(E ;A(B) ) of ea h semi ondu tor. The dipole potential Vdipole equals the di eren e between
the average Hartree potentials. Egap;A(B) is the energy gap of the bulk semi ondu tors.

181

Figure 32: Band stru ture of the fa e- entered ubi Fm3 stru ture of solid C60 as obtained
in LDA (a) and GWA (b). GWA leads to a band gap in good agreement with experiment
and to a 30% in rease in band width of the T1g ; T1u , and Hu bands ompared to LDA. Figure
taken from Ref. [338.

Figure 33: The al ulated self-energy orre tion E QP "LDA is plotted against the quasiparti le energy E QP for a Si4 Ge4 superlatti e, ubi Si, and tetragonally distorted Ge. No
signi ant quantitative di eren e between the self-energy orre tions in the superlatti e and
the bulk materials is found sin e self-energy e e ts in Si and Ge are very lose. All values
are aligned with respe t to the valen e-band edge. Figure taken from Ref. [406.
180

15

Si

GW
LDA

Energy relative to VBM (eV)

10

size of

-5

typical
experimental
error bar

-10

-15

Wave vector

Figure 31: Comparison of LDA and GWA band stru tures along L
X with photoemission
and inverse photoemission experiments for Si. Agreement between theory and experiment is
within the experimental and theoreti al un ertainties. Data are taken from Ref. [342 (full
diamonds), Ref. [347 (open ir les), Ref. [348 (full triangle), Ref. [351 (open triangles), and
Ref. [358 (open diamonds). The typi al experimental resolution is 0.27 eV in energy and
o
0.1 A 1 in momentum ( ompare Ref. [342). The theoreti al error in energy is estimated to
be about  0.1 to 0.2 eV ( ompare Table 21).

179

/npes: minimum size of blocks of G-vectors


n=n
G
n
n
n+1
n+1
first block of r vectors

PE0

in irred. real space cell


images under space
group symmetries
second block of r vectors

PE1

PE2

third block of r vectors

MPI_GATHER
fourth block of r vectors

PE3

Figure 30: Communi ation stru ture for the redistribution of the independent-parti le polarizability over PEs. After the rst 3D FFT ea h PE has the independent-parti le polarizability P 0 (k; r; G0; i ) for one parti ular k-point, a subset of r-ve tors in the irredu ible
real-spa e unit ell as well as their images under symmetry operations of the spa e group, all
G0 -ve tors, and one parti ular time i . As indi ated by the arrows in the gure, MPI GATHER
is used to assemble P 0 for all r-ve tors and a blo k of G0 -ve tors on ea h PE ( rst blo k
on PE0, se ond on PE1, and so on). After the MPI GATHER step des ribed in the gure P 0
is reordered a ording to its r argument to have standard FFT ordering and the se ond 3D
FFT is performed on ea h node. The di erent length of the r-blo ks in the pi ture orresponds to a di erent number of r-points on ea h PE. The total number of G0 -ve tors kept
after performing the rst FFT is nG and npes is the number of PEs used. In the above
example mod(nG ; npes) = 2.
0

178

loop over time


loop over r in irred. unit cell
loop over PEs

PEi

read u nk(r ) for all bands


and all k-points for PEi

PE0

Disk

PE0

Disk

loop over k-points

PE1

read and broadcast u*nk(r) for


one particular k-point, all bands,
and all r

PE2
0
calculate G (r, r, +it)
0
write P (r , r, +it) to disk

loop over PEs

PEi

PE0

Disk

loop over k-points

for each PEi

0
distribute P (r , r, +it)

loop over PEs

over PEs

PEi

PE0

Disk

do 3D FFT to obtain
0
P (k, r, G, it)
redistribute using MPI_GATHER
do 3D FFT to obtain
0
P (k, G, G, it)

loop over PEs

PEi

PE0

Disk

0
write P (k, G, G, it) to disk

Figure 29: S hemati diagram of the ommuni ation stru ture of the parallel implementation
of the real-spa e GWA ode. We list all ommuni ation and al ulational steps needed to
determine the independent-parti le polarizability P 0 in real spa e and imaginary time and
to transform it to re ipro al spa e. The distribution of the unk(r) and of P 0 (r; r0; i ) over all
PEs is des ribed in the text. The redistribution step using MPI GATHER is detailed in Fig. 30.
The Fourier transformation from imaginary time to imaginary frequen y and assembly of
the s reened intera tion via parallel matrix operations is also des ribed in the text.

177

loop over q-points


loop over k-points
loop over PEs

PEi

PE0

Disk

read CBs i*ncb/npes,


(i+1)*ncb/npes -1
from disk and send to
PEi

PE0

Disk

read VB for k-point in


BZq and broadcast to
all PEs

loop over points in BZ q

PE1
PE2

calculate
i
vc
vc
M G (k,q)[MG(k,q)]*
(k,q) =
c v
GG
v,k-q - c,k
i
P

PE1
single-node accumulation
of partial sums at PE0 to
o
calculate P (k,q)
GG

PE0
PE2

Figure 28: S hemati diagram of a parallel al ulation of the independent-parti le polarizability in re ipro al spa e [Eq. (123). The same s heme applies to the al ulation of
the self-energy in re ipro al spa e [Eqs. (117) and (118). PE0 manages disk I/O and distributes the valen e and blo ks of the ondu tion band wave fun tions over all PEs. Ea h
PE al ulates its partial ontribution to the independent-parti le polarizability. The partial
ontributions are summed up at the end of the al ulation via a single-node a umulation
on PE0.

176

-1

Si
25v=0.0

log10 of relative deviation

-2

-3

1v
15c
2c
1c
12c

-4

-5

-6

25

75
125
number of bands in sum over states

175

Figure 27: Convergen e of valen e and ondu tion band energies at the point in Si as a
fun tion of the number of bands in luded in the sum over states of Eq. (118). Convergen e
is smooth with the ex eption of the 02 state whi h is onverged with as little as 40 bands.
60 bands are ne essary for good onvergen e (< 1%) of all energies. The top of the valen e
band is set to zero in ea h ase. The onverged value for ea h energy is approximated by the
energy al ulated with 300 bands. The maximum number of bands available at an energy
ut-o of 8.5 Hartree is about 310. The sum over re ipro al G-ve tors is ut-o at 2.7
Hartree. All other numeri al parameters are identi al to those in Table 18.

175

-1

Si

log10 of relative deviation

-2

25v=0.0

-3

1v
15c
2c
1c
12c

-4

-5

-6

40
80
number of plasmon pole bands

120

Figure 26: Convergen e of valen e and ondu tion band energies at the point in Si as a
fun tion of the number of plasmon pole bands in luded in the sum of Eq. (118). Convergen e
is smooth and 40 plasmon pole bands are su ient to onverge results to within 1%. The
top of the valen e band is set to zero in ea h ase. The onverged value for ea h energy
is approximated by the energy al ulated with 130 plasmon pole bands. The sum over
re ipro al G-ve tors is ut-o at 2.7 Hartree. All other numeri al parameters are identi al
to those in Table 18.

174

Si

25v=0.0

log10 of relative deviation

-1

-2

1v
15c
2c
1c
12c

-3

-4

-5

50
100
150
number of reciprocal lattice vectors in sum

200

Figure 25: Convergen e of valen e and ondu tion band energies at the point in Si as
a fun tion of the number of G-ve tors in the internal sum over G-ve tors in Eq. (106).
Convergen e is smooth and about 100 G-ve tors are su ient to onverge the energies to
less than 1%. The top of the valen e band is set to zero in ea h ase. The onverged value
for ea h energy is approximated by the energy al ulated with 283 G-ve tors orresponding
to a ut-o in re ipro al spa e of 3.9 Hartree. All other numeri al parameters are identi al
to those in Table 18.

173

-1

Si
25v = 0.0

log10 of relative deviation

-2

-3

-4
1v
15c
2c
3
4

-5

-6

20
40
number of k-points in IBZ

60

Figure 24: Convergen e of valen e and ondu tion band energies at the point in Si as a
fun tion of the number of k-points used in the integration of the self-energy [Eqs. (117) and
(118). Convergen e is smooth with the equivalent of 10 k-points in the IBZ being ne essary
to onverge the low-lying 015 and 02 to better than 1%. The top of the valen e band is set
to zero in ea h ase. The onverged value for ea h energy is determined by Shanks iteration
[321. All other numeri al ut-o s are given in Table 18.

172

Im
Re

< (i)> (eV)

-2

Im

10

Re

< ()> (eV)

20

-10
-60

-40

-20

0
20
(eV)

40

60

Figure 23: Energy-dependent orrelation ontribution to the self-energy of Si as a fun tion of


imaginary (upper panel) and real (lower panel) frequen y. The expe tation value of C has
signi antly less stru ture along the imaginary axis ompared to the real axis allowing the
use of Fast Fourier Transforms with equidistant frequen y and time grids to swit h between
imaginary time and frequen y. Figure adapted from Ref. [103.

171

Figure 22: Can ellation between vertex (V) and self- onsisten y (SC) orre tions to the
diagonal elements of the RPA stati polarizability PGG(k; ! = 0) (in Rydberg a.u.) for
sili on and diamond. Lowest-order vertex and self- onsisten y orre tions as onsidered in
Ref. [119 largely an el leading to an overall enhan ement of the RPA polarizability by
15%. The onstant ontributions of the vertex and self- onsisten y orre tions to the
head element of the RPA polarizability matrix for k ! 0 an el, whi h ensures the orre t
s reening behavior in semi ondu tors. Figure taken from Ref. [119.

170

Figure 21: Left panel: RPA polarizability and orre tions to rst order in the s reened intera tion W . SC1-SC4 denote orre tions due to self-energy insertions in the Green fun tion,
i.e., due to lowest-order self- onsisten y e e ts. V orresponds to a ladder diagram whi h is
the lowest-order vertex orre tion. The solid dire ted line denotes the LDA Green fun tion.
The ross denotes Vx and the wiggly line denotes the RPA-dynami ally-s reened intera tion. Right panel: GWA self-energy plus lowest-order self- onsisten y (SC1-SC4) and vertex
(V) orre tions. The diagrams SC3 and SC4 are self-energy orre tions due to lowest-order
orre tions to the valen e density. The wiggly line denotes the dynami ally s reened intera tion whi h an be evaluated either in RPA or in RPA+V+SC. The notation is otherwise
identi al to the one used in the left panel. The gure has been taken from Ref. [119.

169

Figure 20: Band narrowing relative to the independent-parti le band width vs. ele tron
density parameter rs for the homogeneous ele tron gas and several approa hes to the determination of the self-energy. A positive value orresponds to an a tual narrowing of the
bands. The two dashed lines orrespond to a standard (RPA) GWA al ulation (in whi h
vertex orre tions are negle ted in the diele tri fun tion " and the self-energy ) and a
GWA al ulation in whi h vertex orre tions are in luded only in " ( = 1). The solid
line orresponds to a al ulation that in ludes vertex orre tions in both " and  using a
Vashista{Singwi many-body lo al- eld fa tor [264. This urve is universal in the sense that
it is hardly a e ted by a hange of the many-body lo al- eld fa tor. The = 1 al ulation
leads to band narrowing that is about twi e as large as the RPA band narrowing for metalli
densities (rs  2 6) and ompares favorably with experiments for simple metals. Adding
onsistent vertex orre tions to the self-energy an els the e e t of vertex orre tions in the
diele tri s reening giving results in lose agreement with RPA. Figure taken from Ref. [240.

168

Figure 19: The quasiparti le dispersion Ek for a fully self- onsistent GWA al ulation (solid
line), a partially self- onsistent GW0 A al ulation (dashed line), a standard G0 W0 A al ulation (dotted line), and for non-intera ting ele trons (dashed-dotted line). Only the standard
G0 W0 A al ulation leads to band-width narrowing in omparison to the free-ele tron result. However, this observed band-width narrowing is too small to explain experimentally
observed narrow band widths in simple metals. Self- onsisten y in reases the band width in
omparison to free ele trons and hen e leads to in reased deviation from experiment. Data
shown orresponds to rs = 4 and is taken from Ref. [231.

167

Figure 18: De ay rate k of jellium at rs = 4 determined by a fully self- onsistent GWA


al ulation (solid line), a partially self- onsistent GW0 A al ulation (dashed line), and a
standard G0 W0 A al ulation (dotted line). The two latter results show a region with mu h
larger de ay rate (shorter lifetime) aused by inelasti ollision with plasmons. This physi ally orre t feature is absent from the fully self- onsistent GWA result. Figure taken from
Ref. [231.

166

Figure 17: The quasiparti le weight Zk for jellium at rs = 4 determined by a fully self onsistent GWA al ulation (solid line), a partially self- onsistent GW0 A al ulation (dashed
line), and a standard G0 W0 A al ulation (dotted line). Self- onsisten y leads to a systemati
in rease in quasiparti le weight and to a loss of stru ture due to the suppression of plasmon
satellites in the fully self- onsistent result. Figure has been taken from Ref. [231.

165

Figure 16: Fully self- onsistent one-parti le spe tral fun tion A(k; ! ) for the homogeneous
ele tron gas evaluated at k = kF , rs = 4, T=0 (Ref. [231, upper panel) and at k = 0:99kF ,
rs = 5, nite T (Ref. [235, lower panel). The results in the upper panel are ompared with a
partially self- onsistent spe tral fun tion obtained from a GW0 A al ulation [237. Those in
the lower panel are ompared with results obtained after the rst and third iteration towards
self- onsisten y. Both al ulations show that self- onsisten y (i) sharpens and in reases the
weight of the quasiparti le peak (see also Fig. 17), and (ii) redu es the spe tral weight of
the plasmon satellite peaks. The two self- onsistent al ulations di er in the shape of the
plasmon peaks.

164

Figure 15: Left panel: Sili on quasiparti le energy shifts Eqp ELDA as a fun tion of the LDA
energy ELDA . The overall shape of the energy shifts is similar to the shape of quasiparti le
energy shifts in jellium [4, 229 (not shown) and Ag (see Fig. 42 and Se tion 26 a). Right
panel: Diagonal matrix elements of the imaginary part of the Si self-energy with respe t
to LDA orbitals al ulated at the energy of the orresponding quasiparti le peak. The
shape of the imaginary Si self-energy is similar to the shape of the non-self- onsistent de ay
rate of jellium (see Fig. 18). In both gures, the full ir les are the result of a standard
(RPA) GWA al ulation, the empty ir les have the (time-dependent) LDA vertex fun tion
in luded (GW al ulation, see Se tion 14). The self-energy is al ulated along the L- -X
line. Figure taken from Ref. [102.

163

2.0
Si
SiC
GaN

(k) at and at 10
special k-points

(k) (eV)

1.5

1.0

0.5

4
5
6
Wave Vector

10

Figure 14: Self-energy orre tion (k) = h(E ) Vx LDA i to the dire t band gap at the
x
point and at 10 spe ial
k-points in the f Brillouin zone for Si, SiC, and GaN. The standard
deviation from the average self-energy orre tion (the \s issors" shift) amounts to 0.03 eV
for Si, 0.13 eV for SiC, and 0.17 eV for GaN. This orresponds to 4.5%/10.4%/11.7% of
the average self-energy orre tion (0.73 eV/1.20 eV/1.47 eV for Si/SiC/GaN). Although the
s issors approximation works well for ovalently bonded Si, it learly breaks down for more
ioni materials su h as SiC and GaN.

162

Figure 13: Matrix elements of the ele tron self-energy operator evaluated in the GWA drawn
as a fun tion of energy for sele ted states near the band gap are displayed for (a) diamond,
(b) Si, ( ) Ge, and (d) LiCl. The quasiparti le energies of these states are indi ated on the
energy axis. The self-energy shows an approximately linear dependen e on energy lose to
the quasiparti le energy for all states and all materials onsidered. The slope of h(E )i is
roughly material- and state-independent and amounts to about 0.2. This indi ates, that
dynami al e e ts are important for a quantitative des ription of quasiparti le energies in
solids. Figure taken from Ref. [44.

161

Figure 12: (a) The real part of the matrix elements of the GWA self-energy operator of sili on
h(E )i and the LDA ex hange- orrelation potential hVx LDAi plotted against the quasiparti le
energy E . (b) The di eren es h(E ) Vx LDA i (essentially the quasiparti le energy orre tion)
and h(0) Vx LDA i of sili on plotted against the quasiparti le energy. The energy dependen e of the self-energy must be taken into a ount to obtain the orre t dispersion for the
quasiparti le energies. ( ) For omparison, h(E ) Vx LDA i and h(0) Vx LDA i are plotted
against the quasiparti le energy E for jellium at the average density of sili on (rs = 2). The
Fermi energy EF is aligned with the middle of the band gap. Both are relatively featureless
and learly do not share the sharp dis ontinuities present in (a) and (b). (d) The real parts
of the matrix elements of the bare-ex hange (Hartree-Fo k) self-energy operator of Si hX i
and the stati ally s reened ex hange self-energy operator hSSX i. hVx LDAi is subtra ted as
in (b). The non-lo ality of X has too large a range due to the negle t of s reening whi h
leads to a jump in the self-energy orre tions at the Fermi level that is too large in omparison with experiment. (e) The real parts of the matrix elements in sili on and jellium (rs =
2) of the frequen y derivative of the self-energy h (! = midgap)=! i. Figure taken from
Ref. [185.
160

Figure 11: Contour plots of the self-energy (r; r0 ; E = midgap) in eV a.u. 3 for r xed at
the bond enter and r0 shown in the (110) plane for (a) Si, (b) GaAs, ( ) AlAs, and (d)
diamond. For sili on, the orresponding plots with r xed at the tetrahedral interstitial site
is also shown [panel (e). For omparison, the self-energy operator of jellium with rs = 2
(the average density of sili on) is shown [panel (f). Godby, S hluter, and Sham suggest to
model the approximate form of the non-lo ality of the self-energy (not its depth) using the
results from jellium al ulations. Figure taken from Ref. [185.

159

Figure 10: Contour plot in the Si (110) plane of of the s reening potential W s r (in Rydberg)
in response to a single ele tron (indi ated by a ross) at (a) a bond- entered or ( ) an
interstitial site. Panels (b) and (d) show the orresponding lo al- eld (LF) ontributions.
Lo al elds (i) ontribute between 1/3 (bond enter) and 1/10 (interstitial) to the total
s reening potential, (ii) are responsible for the asymmetry of the s reening potential, and
(iii) are short-ranged and be ome negligible after one bond length. Figure adapted from
Ref. [44.

158

Figure 9: Plot of the self-energy (r; r0 ; E = midgap) of Si where r is hosen to lie at the
bond enter and r0 is varied along the [111 dire tion. Atomi positions are indi ated by
losed ir les and v ( ) denotes the real part of the highest-lying valen e (lowest-lying
ondu tion) band wave fun tion lose to the point al ulated in the LDA. The range of nonlo ality of the self-energy is about one bond length. It follows from the gure, that h v jj v i
is large and negative whereas h jj i has large positive and negative ontributions due
to the non-lo ality of the self-energy and the nodal stru ture of the ondu tion band wave
fun tion. Hen e, the self-energy pulls the valen e band deeper in energy with respe t to the
ondu tion band and the band gap opens up in omparison to the LDA. Figure taken from
Ref. [6.

157

Figure 7: Stati diele tri fun tion "(q; ! = 0) as a fun tion of the re ipro al latti e ve tor
q for Si and GaAs. The model diele tri fun tion of Cappellini et al. [104 (solid line)
ompares better with RPA results of Walter and Cohen [105 ( losed boxes for q along the
(111) dire tion, open boxes for q along the (100) dire tion) than the Levine-Louie model
diele tri fun tion (dashed line) [106. RPA results by Balderes hi and Tosatti (stars) [107
for large q seem to favor the Levine-Louie model over the model by Cappellini et al. The
parameters and "(0) are the same as in Eq. (49). Figure adapted from Ref. [104.
3
3

+
3

Coulomb repulsion
Coulomb attraction

Figure 8: The irredu ible ele tron-hole intera tion in the time-dependent Hartree-Fo k
approximation is given by the sum of a s reened Coulomb attra tion and an uns reened
Coulomb repulsion. The rst term generates an in nite sum of ladder diagrams whereas the
se ond term generates an in nite sum of polarization bubbles ( ompare Eq. (77)). Taken
from Ref. [168.
156

0.5*[(k F +q)2-k 2]
F

Energy

Plasmon
pole model
Plasma mode
2
0.5*[(-k +q)2 -k ]
F
F

pl

Single Particle
Excitations
0

2k F

qc

reciprocal lattice vector q

Figure 6: Spe trum of ex itation energies vs. wave ve tor transfer q for a homogeneous,
intera ting ele tron gas. The upper (lower) boundary of the single-parti le ex itations is
0:5[(kF + q )2 kF2 (0:5[( kF + q )2 kF2 ). In simple plasmon-pole models this spe trum is
repla ed by a single mode !pl (q ) indi ated by the dotted line. The real plasmon mode (full
line) is the dominant ex itation for small q -ve tors (0  q < q ). Beyond q , the plasmon is
heavily damped (dashed line). The gure is adapted from Ref. [93.

155

Figure 5: Left panel: Numeri al results obtained using the empiri al pseudopotential te hnique for various elements of the real ("1 ) and imaginary ("2 ) parts of the diele tri matrix
"GG (q; ! ) as a fun tion of frequen y for Si (solid line). The real part of the HybertsenLouie plasmon-pole model is plotted for omparison (dashed line). The model repla es the
peaked stru ture in "2 (! ) by a -fun tion, is onstru ted to des ribe the limits ! ! 0 and
! ! 1 orre tly, and breaks down for intermediate frequen ies. Right panel: Real part of
the inverse diele tri fun tion of Si derived from the numeri al, empiri al-pseudopotentialbased results by Walter and Cohen [92 in omparison to the Hybertsen-Louie plasmon-pole
model. The average behavior of the inverse diele tri fun tion is aptured rather well by the
plasmon-pole model for energies below the plasmon energy of Si (!pl = 16.7 eV). Figures are
adapted from Ref. [44.
0

154

a)

=GW

b)
G=G +G G
0

G=G +G G
0

G
=1+(/G)GG

=GW

LDA

G = G or G

HF

P=GG

W=v+WPv

P=GG

W=v+WPv

Figure 4: a) S hemati representation of the iterative determination of the self-energy  using


Hedin's equations (Eqs. (21)) in onjun tion with Dyson's equation (Eq. (16)). Entries in
boxes symbolize the mathemati al relations that link , G, , P , and W . Starting with  = 0
leads to an RPA s reened intera tion W and subsequently to  = GW RP A. b) S hemati
representation of the self- onsistent determination of the self-energy in the GWA. P , W , and
 are onstru ted starting from an LDA or Hartree-Fo k independent-parti le propagator.
Subsequently,  updates the quasiparti le wave fun tions and energies and a new Green
fun tion G is determined. This pro ess is repeated until self- onsisten y is rea hed. Most
pra ti al appli ations either determine only the quasiparti le energies self- onsistently or
do not update quasiparti le energies and wave fun tions at all. Self- onsisten y of GWA
al ulations is dis ussed in Se tion 13.

153

-2

Energy gap (eV)


4

Si; 42
Ge; 43
diamond; 44
3C SiC; 42
LiCl; 44
-C3N4; 45
BN; 46
BP; 46
BAs; 46
AlN; 47
AlP; 48
AlAs; 43
AlSb; 48
GaN; 42
GaP; 48
GaAs; 43
GaSb; 48
InP; 48
InAs; 48
InSb; 48
Al0.5Ga0.5As; 48
In0.53Ga0.47As; 48
GaAs0.5N0.5; 49
GaAs0.75N0.25; 49
ZnO; 50
ZnS; 51
ZnSe; 51
ZnTe; 51
CdS; 52
CdSe; 51
CdTe; 51
MgO; 53
MnO; 54
NiO; 55
CaCuO2; 54
Li2O; 56
ZrO2; 57
SnO2; 58

LDA
GWA
Expt., indirect gap
Expt., direct gap

Figure 3: Comparison of hara teristi dire t and indire t LDA, GWA, and experimental
energy gaps for all semi ondu tors and insulators for whi h rst-prin iples GWA al ulations
have been reported. GWA orre ts most of the LDA band gap underestimation over more
than one order of magnitude in the experimental band gap. The values for MnO, ZnO,
and CaCuO2 are from model-GWA al ulations, whi h are a urate to within 0.4 eV. The
dis repan y between GWA and experiment for LiO2 results from the negle t of ex itoni
e e ts. The experimental value for BAs is tentative. The referen es for the LDA, GWA,
and experimental values are listed after the element symbols.

152

10

Ekin

b)

Ekin
h

Vacuum

a)
Source

ele

ph

ctr

on

n
oto

Source

el

ro
ect

Sample p
h

Analyzer

A
CB

oto

Analyzer

photon -> electron:

photoelectron spectroscopy

electron -> photon:

inverse photoemission

E gap

h
VB
photoelectron

inverse

spectroscopy

photoemission

N -> N - 1

N -> N + 1

Figure 2: a) S hemati representation of an (inverse) photoemission experiment; b)


S hemati representation of the ex itation pro ess in a photoemission (left) and inverse
photoemission (right) experiment. The energy of the in oming (outgoing) photon is h ,
the ele tron kineti energy Ekin, Egap is the band gap, EA the ele tronegativity, and E
the photothreshold energy of the sample. Dire t photoemission measures the quasiparti le
properties of o upied bands and de reases the total number of ele trons N in the system.
An in oming photon eje ts a valen e band (VB) ele tron out of the sample. The ele tron
energy is measured and the valen e band energy an be obtained via Ekin = EV B + h .
Inverse photoemission measures the properties of quasiparti les in uno upied bands. An
in oming ele tron of energy Ekin impinges on the sample and loses energy via emission of a
photon h . The ele tron rea hes an energeti ally lower available ondu tion state leading to
Ekin = ECB + h .

151

A(E)

non-interacting
interacting

Im ( E)
E

Figure 1: S hemati representation of the spe tral fun tion A(E ) (Eq. (8)) for a nonintera ting and an intera ting many-body system. The di eren es between the two ases are
(i) the real part E~ of the quasiparti le energy E = E~ + i is shifted with respe t to the bare
energy ", (ii) the quasiparti le a quires a nite life time 1= due to intera tion ompared to
the in nite life time of the non-intera ting parti le, and (iii) the spe tral weight Z (shaded
area) of the quasiparti le peak is less than unity due to redistribution of spe tral weight
into the in oherent ba kground (Im(E )) whereas the spe tral weight of the bare parti le is
unity. The hemi al potential is .

150

Method
Si
Expt.
3.4
LDA
2.6
GWA
3.3
HF
8.7
a
EXX-KS 3.3 /2.9b
EXX+x
9.6a
KLI-KS
2.9
sX-LDA
3.4e
Frits he 3.7f /3.2g
QMC
3.7h/3.9i

Ge
C GaAs
0.9
6.5/7.3
1.5
0.3
5.5
0.2
0.8
7.6
1.5
7.9
14.6
9.1
b
a
b
1.6 6.3 /5.9
|
a
|
15.6
1.3d
| 1.9d
0.3e
| 1.1e
| 6.5f /6.4g
|
|
|
|

a Ref. [609, b Ref. [607, Ref. [604, d Ref. [605, e Ref. [610,
f Ref. [611 with Gaussian ex hange- orrelation hole,
g Ref. [611 with Lorentzian ex hange- orrelation hole,
h Ref. [612 { Di usion MC, i Ref. [613 { Variational MC.

Table 39: Dire t band gaps in eV at for density-fun tional methods that go beyond LDA
ompared to experiment, GWA and Hartree-Fo k: EXX-KS { Kohn-Sham orbital gap with
exa t ex hange; EXX+x { full band gap with exa t ex hange in luding the gap dis ontinuity x ; KLI-KS { Kohn-Sham gap with the simpli ed exa t-ex hange method of Krieger, Li,
and Iafrate; sX-LDA { generalized non-lo al Kohn-Sham formulation with s reened ex hange
and lo al-density approximation of orrelation; Frits he { Frits he's generalized density fun tional theory for ex ited states; QMC { quantum Monte Carlo band-stru ture method. For
Si, Ge, and GaAs, the experimental and LDA values are from olumns 5 and 4 in Table 33,
while the GWA values are the sum of the LDA gap and the GWA- orre tion in the last
olumn of Table 34. For diamond, the values are from Table 14 omplemented with the
experimental value (6.5 eV) quoted in Ref. [614 to illustrate the rather large experimental
un ertainty. The Hartree-Fo k gaps are from Ref. [615 for Si, Ge, and C, and from Ref. [616
for GaAs.

149


d = (2) =2 (pm/V) =(h! )2 (deg/[mm (eV)2 )
No LF LF
Expt.
No LF LF Expt. No LF LF
Expt.
a

Se
9.0
7.9 7:3  1:1
78
111 9725
21
55 56  30
-quartz 2.42 2.30
2.35b
0.35 0.33 0.34d
0.7
5.6 4:6  0:1
a Ref.

[142, b Ref. [580, Ref. [581, d Ref. [582

Table 38: Lo al- eld (LF) orre tions for selenium and -quartz (SiO2) in diele tri onstant
, se ond-harmoni oe ient d, and opti al rotatory power  [543, 583. Modest lo al- eld
orre tions for  do not imply modest orre tions in the other opti al properties. Note also
that for both d and  the sign of the lo al- eld orre tion di ers between Se and quartz.
For the se ond-harmoni oe ient d, there are more experimental results than quoted in
the table. For selenium these experimental values vary substantially, while for quartz the
di erent values are in good agreement. We refer to Ref. [543 for a more detailed dis ussion
and referen es. The quoted experimental values for the rotatory power are the zero-frequen y
limits given in Ref. [583, whi h were extrapolated from the data of Refs. [584, 585 (Se) and
Ref. [586 (quartz).

148

LDA S iss ()


Expt.
C
5.9 5.2 (1.8 eV)
5.7a
SiC
6.9 6.1 (1.2 eV)
6.5a
GaN 5.5 4.8 (1.5 eV) 5.350.20b
a Ref.

[182, b Ref. [559

Table 36: Diele tri onstants for large-gap insulators in LDA and within the s issors-shift
approa h. The C and SiC values are from Ref. [540 and the GaN values are from Refs. [542
(LDA) and [560 (S iss). The s issors shifts , derived from averaged GWA orre tions, are
shown within paranthesis. The GWA-based s issors-shift approa h systemati ally over orre ts the somewhat too large LDA values.

omp. LDA No LF
GaP
xyz
65
46
GaAs
xyz 205
106
AlP
xyz
21
17
AlAs
xyz
35
24
SiC
xxz 6.6
4.9
zzz 4.7
2.7
GaN
xxz 3.2
2.7
zzz 5.4
4.2
a Ref.

LF Expt.
38 372a
95 815a
14
22
4.4
3.1
2.1 2.6b
3.5 5.4b

[571, b Ref. [572


Table 37: Se ond-harmoni oe ient d = (2) =2 in pm/V in LDA and within the s issorsshift approa h without (No LF) and with (LF) lo al- eld orre tions [573. The se ond
olumn shows whi h tensor omponent is being tabulated. The lo al- eld orre tion is
typi ally of order 15%, but is +13% (absolute value) in the SiC zzz omponent.

147

Egap
LDA
Si
0.8
Ge
1.2
GaAs
1.3

PT
0.7
0.6
0.7

GW
gap
UE
0.7
0.8
0.9

CP
0.7
1.1
1.3

Table 34: GWA orre tion (in eV) to LDA dire t gap at with di erent levels of approximation in the GWA al ulation: PT { perturbation theory with LDA bandstru ture; UE
{ self- onsistently updated band energies; CP { in lusion of ore-polarization e e ts. The
rst olumn is the LDA gap error given by the di eren e between the last two olumns in
Table 33. The GWA values are from Tables 21, 22, and 23 in Se tion 18.

LDA No LF LF Expt.
Si
13.5 11.7 11.2 11.4a
Ge
22.0 16.6 16.0 15.3a
GaAs 13.7 11.7 11.2 10.8b
GaP 10.4
9.3
8.8 9.0b
AlAs
9.5
8.7
8.1 8.2b
AlP
8.3
7.8
7.2 7.4b
a Ref.

[557, b Ref. [558

Table 35: Diele tri onstants for small- and medium-gap semi ondu tors in LDA and within
the s issors-shift approa h without (No LF) and with (LF) lo al- eld orre tions [536, 541.
The values in luding lo al- eld orre tions are all within 5% of experiment.

146

NR
Si
2.7a;b
Ge
0.7a;b
GaAs 1.1a;b

SR-PP
2.6 ;d
0.0g
0.6d;g;h;i

Egap (eV)
FR-PP
FR-CR
2.6 ;e
2.6e;f
0.1 ;e
0.3e;f
0.5 ;e;g;h 0.2e;f;g;j

Expt.
3.4n
0.9n
1.5n

a Ref. [544, b Ref. [545, Ref. [114, d Ref. [185, e Ref. [43,
f Ref. [546, g Ref. [192, h Ref. [121, i Ref. [541, j Ref. [547,
k Ref. [548, l Ref. [549, m Ref. [550, n Ref. [551

Table 33: Dire t LDA band gap (in eV) at with di erent levels of approximation: NR {
nonrelativisti ; SR{PP { s alar relativisti pseudopotential (with atomi 3d ore); FR{PP
{ fully relativisti pseudopotential; FR{CR { fully relativisti with ore relaxation. The
tabulated values re e t medians of a multitude of published values. Typi ally, a parti ular
referen e will have values within 0.15 eV of the tabulated ones. However, despite variations
in absolute values the relative trends agree between di erent referen es.

145

rs
Al
Li
Na
K

2.1
3.3
4.0
4.9

Northrup et al. Shirley Shung et al.


Expt.
Ref. [184, 258 Ref. [232 Ref. [265
LDA GWA
GWA
RSPT
10.0
10.2
10.6a
3.5
2.9
3.1
3.0b
3.2
2.5
2.7
2.5
2.650.05
2.3
1.6
1.9
1.5
1.4d
Ref. [508, b Ref. [509, Ref. [506, d Ref. [510.

Table 32: Comparison between experimental and theoreti al o upied band width (eV)
obtained with (i) vertex orre tions in the diele tri matrix " only and use of self- onsistent
quasiparti le energies [184, 258, (ii) partial self- onsisten y, stati vertex orre tions in "
and dynami vertex orre tions in the self-energy  [232, and (iii) non-zero imaginary part
of  and surfa e e e ts [229, 265. Agreement with experiment is generally good. However,
self- onsisten y e e ts not taken into a ount in the above al ulations may widen the Na
band width by an estimated 0.4 to 0.7 eV based on results of Ref. [231 and shift the
theoreti al results towards the nearly-free-ele tron and LDA band width values. The results
for Ref. [265 are presented as an average over the range of band widths given. rs is the
Wigner-Seitz radius of an ele tron gas with identi al average density than the simple metals.

144

Ionization potentials

Promotion
energy
s2 p(2 P ) s2 (1 S )
s2 p(2 P )
s2 p(2 P )
! s2(1 S ) ! s(2 S ) ! sp(3 P ) ! sp2(4 P )

HF
7.5
23.8
10.4
2.0
GWA
8.5
24.9
12.0
2.8
LSDAa 8.6, 8.6b
24.6
12.7
3.2
Expt.
8.3
25.2
12.9
3.6
Al
HF
5.3
17.8
8.5
2.1
GWA
6.0
18.9
10.0
3.0
LSDAa 6.0, 6.0b
18.9
10.7
3.6
Expt.
6.0
18.8
10.6
3.6
Ga
HF
5.3
19.0
9.5
2.9
GWA
6.0
20.0
11.2
4.1
LSDAa
6.1
20.8
12.3
5.0
Expt.
6.0
20.5
12.0
4.8
Ref. [481 unless otherwise noted, b Ref. [482, as ited in Ref. [67,
for further referen e see Refs. [483 and [484.

Table 31: First and se ond ionization potentials and sp-promotion energies in GWA, HartreeFo k (HF), lo al spin density fun tional theory (LSDA), and experiment for the group-III
elements boron, aluminum, and gallium. GWA improves upon Hartree-Fo k but errors of
about 20% in the s ! p promotion energies remain ompared to an error of about 5% in
LSDA. Improvement of GWA ionization potentials over LSDA is marginal. All energies are
in eV. Table adapted from Ref. [67.

143

state
0.85 X1
X1
L1
15
0
2

Expt.

Zhu [462
Godby [463
LDA GWA LDA GWA
1.6,a 1.4a;b 1.41 1.32 1.3 1.8
1.73 1.68 0.9 1.6
3.95 4.06
0.59 0.53 0.5 0.6
11.9 12.2
a Ref. [182, b Ref. [464.

Table 30: The pressure derivatives of Si band gaps (eV/Mbar) at equilibrium in LDA,
GWA, and experiment. In parti ular, the data of Zhu et al. [462 shows that LDA pressure
derivatives are (i) in good agreement with experiment, and (ii) in good agreement with
GWA. The theoreti al results of Ref. [463 are a urate to within 0.3 eV/Mbar [463.
Table adapted from Refs. [462, 463.

142

LDA
GWA
Ga 3d ore Ga 3d valen e
Co iorva [196
0.62
0.93
1.18
Albanesi [420
0.85
Ke [421
0.81
Expt.
0.700.24a
1.360.07b
a Ref. [422, b Ref. [423.
Table 28: Valen e band o set in eV at the non-polar, zin blende GaN/AlN(110) interfa e
using the average latti e onstant of AlN and GaN and pseudopotentials with the Ga 3d
ele trons treated either as ore or as valen e ele trons [196 or LMTO [420, 421. In lusion
of the Ga 3d ele trons as valen e ele trons (i) leads to agreement between the three LDA
al ulations, and (ii) hanges the sign of the interfa e dipole [196. The self-energy orre tion
of 0.25 eV equals about 30% of the LDA valen e band o set and has been estimated from
bulk al ulations that treat the Ga 3d ele trons via nonlinear ore orre tions [196 (see
Se tion 15 a for a dis ussion of the treatment of d ele trons in GWA). The experimental
values refer to wurtzite interfa es.

k-point

K

M

LDA GWA Expt.a


3.22 3.82 3.80
4.29 4.76 4.78
7.85 8.47 8.64
3.87 4.63 4.76
a Ref. [436.

Table 29: LDA, GWA, and experimental energies of Si(111):H (11) surfa e states at K and
M (eV) with respe t to the valen e band maximum. The GWA orre ts LDA energies by
0.5 to 0.8 eV. LDA underbinds strongly lo alized states due to unphysi al self-intera tions
whi h are eliminated in the GWA. Table adapted from Ref. [429.

141

Compound Aryasetiawan
Massidda
LDA+Ua SICb
Expt.
LSDA GWA LSDA GWA
Energy gaps (eV)
MnO
1.0
4.2
3.5
3.98
3.8-4.2 ;d
NiO
0.2
5.5
0.3
3.7
3.1
2.54
4.3e , 4.0f
CaCuO2
0.0
1.4
2.1
1.5g
Magneti moments (B )
MnO
4.29
4.52 (4.52) 4.61
4.49 (4.49)
4.58j
k
NiO
1.0
1.6
1.12
1.56 (1.83) 1.59
1.53 (1.80) 1.77 , 1.64l , 1.90j
CaCuO2
0.42
0.66
0.51m
a Ref. [382, b Refs. [383 and [384, Ref. [385, d Ref. [386, e Ref. [387, f Ref. [388, g
Ref. [389, j Ref. [390, k Ref. [391, l Ref. [392, m Ref. [393.
Table 27: Energy gaps (eV) and magneti moments (B ) for transition-metal oxides obtained
in ab-initio GWA (Aryasetiawan, Ref. [55), model GWA (Massidda, Refs. [50, 54), and lo al
spin density (LSDA) fun tional al ulations in omparison to experiment, LDA+U al ulations, and self-intera tion- orre ted (SIC) al ulations. GWA agreement with experiment
is better than or at least as good as in LDA+U or SIC. Due to the large GWA orre tions
to LSDA in the transition metals, self- onsisten y in the GWA wave fun tions is required
to get good agreement with experiment. Values in parentheses for the magneti moments
in lude the orbital ontribution. Table adapted from Ref. [54.

140

Ref.
Expt.
Aulbur [42
Palummo [367
Rubio [47
Aulbur [42
Palummo [367
Rubio [47
Aulbur [42
Palummo [367
Rubio [47

1v

15.5

16.7

16.3

17.8

X1v
12.4 13.5
13.0 14.8
L1v
13.2 14.3
13.8

15.5

15v
0.0
0.0 0.0
0.0 0.0
0.0 0.0

1
3.2a ,3.3b

15

2.0 3.1
1.9 2.8
2.1 3.1

10.5 12.0
10.2 11.3
10.6 12.2

X3v
6.1 6.8
6.2 6.8
6.5 6.9
L1v
6.8 7.6
7.0 7.5
7.4 7.8
Ref. [368, b

X5v
2.4 2.7
2.6 2.9
2.8 3.0
L3v
0.8 0.9
0.9 1.0
1.0 1.1
Ref. [369.

X1
3.3 4.4
3.2 4.0
3.2 4.7
L1
4.8 6.1
4.7 5.7
5.0 6.2

Comments

X1
6.7 8.1
6.6 7.7
6.9 8.4
L1
8.9 10.8
8.9 10.4
9.1 11.2

"RP A , TM
"RP A , BHS
"model , update GF,
HSC(Ga), TM(N)
X3
X5
11.9 14.0 14.2 16.1
12.2 14.5 14.6 16.7
L3
10.5 11.9
10.3 11.3
10.6 12.3

Table 26: GaN energies at high symmetry points, same notation as in Table 21. The
di erent al ulations of the LDA and GWA energies for both the valen e band maximum
and ondu tion band minimum di er by 0.1 to 0.4 eV and by 0.2 to 0.7 eV, respe tively.
Taking all states into a ount leads to a variation of 0.1 to 0.8 eV for LDA and 0.1 to
1.3 eV for GWA. All al ulations are pseudopotential-plane-wave based and use a rstprin iples RPA diele tri matrix with the ex eption of Rubio et al. [47 who use a model
diele tri matrix. The model diele tri matrix is usually a urate to within 0.1 to 0.4 eV
and annot a ount for all the di eren es in the data. Further deviations may result from
the di erent hoi e of the nitrogen pseudopotential. BHS stands for Ba helet{Hamann{
S hluter [324 pseudopotentials as implemented by Stumpf, Gonze and S heer [370, HSC
stands for Hamann{S hluter{Chiang pseudopotentials [371, and TM for Troullier{Martins
pseudopotentials [325, 372. All energies are in eV.

139

X3
L3v
X5v
X5v
L3v
L3v
1
15
X5v
X1
L1
K

Expt.a
Aulbur [42 Rohl ng [114 Ba kes [130
X1
3.10
3.04
3.25 (3.09)
3.18
X1
3.55
3.40
3.55 (3.49)
3.48
X1
6.0
5.72
5.96 (5.83)
5.79
X3
8.3
8.76
9.21 (8.92)
8.97
L3
9.7
9.46
9.78 (9.70)
9.79
b
L 1
7.5
7.51
7.74 (7.64)
7.87
7.4b
7.19
7.35 (7.29)
7.81
7.75
8.18
8.35 (8.42)
8.66
3.4b
3.53
3.62 ( 3.52) 3.42
2.39, 2.417 2.19
2.34 (2.31)
2.37
4.2
6.30
6.53 (6.46)
6.76
4.00
Ref. [361 unless otherwise noted, b Ref. [363, Ref. [364.

Table 25: Comparison of ubi SiC quasiparti le energies for plane wave al ulations [42, 130
and a Gaussian orbital approa h [114 with experimental energies at high-symmetry points.
Agreement with experiment is good for all three GWA al ulations. Average deviations are
0.22 eV [42, 0.24 eV (Ref. [114, 0.20 eV if 60 Gaussians are used), and 0.29 eV [130. In reasing the onvergen e of the Gaussian-orbital-based al ulation by keeping 60 (Ref. [295,
numbers in parentheses) rather than 40 (Ref. [114) Gaussians moves the quasiparti le energies onsistently towards the onverged results of the plane wave al ulation of Ref. [42.
Experimental values are taken from Ref. [361 unless otherwise noted. All energies are given
in eV.

138

Table 23: GaAs energies at high symmetry points, same notation as in Table 21. The LDA
and GWA energies at , X , and L for the lowest ondu tion band vary between the listed
al ulations by 0.4 to 0.6 eV in LDA and 0.3 to 1.0 eV in GWA due to (i) in lusion of ore
relaxation and polarization in Refs. [43, 290, (ii) insu ient onvergen e (Ref. [114, see
Table 15), (iii) use of the atomi sphere approximation and negle t of ombined orre tions
[290, and (iv ) update of Green fun tions in Refs. [43, 121 in ontrast to Refs. [42, 114, 290,
360. The e e ts of these approximations are dis ussed in Se tions 15 and 18 in the text. All
al ulations use plane waves unless noted otherwise. For an explanation of the omments in
the table, see Tables 21 and 22. All energies are given in eV. Spin-orbit splitting is negle ted
in the experimental data. Most of the experimental data are at room temperature.

Ref.
Aulbur [42
Rohl ng [114
Ba kes [130
Aulbur [42
Rohl ng [114
Ba kes [130
Aulbur [42
Rohl ng [114
Ba kes [130

1v
15.34 16.08
15.44 16.44
15.07 16.13
X1v
10.22 10.96
10.31 11.24
10.12 11.19
L1v
11.71 12.46
11.80 12.75
11.57 12.65

15v
0.00 0.00
0.00 0.00
0.00 0.00
X3v
7.82 8.44
7.89 8.64
7.70 8.38
L1v
8.56 9.19
8.63 9.42
8.45 9.15

1
6.21 7.19
6.41 7.35
6.57 7.81
X5v
3.20 3.53
3.22 3.62
3.06 3.42
L3v
1.06 1.21
1.06 1.21
0.98 1.11

15
7.16 8.18
7.16 8.35
7.24 8.66
X1
1.31 2.19
1.31 2.34
1.22 2.37
L1
5.33 6.30
5.46 6.53
5.46 6.76

X3
4.16 5.23
4.33 5.59
4.14 5.55
L3
7.12 8.25
7.20 8.57
7.12 8.68

X5
13.78 15.23
14.05 15.78
13.93 16.05
L1
9.90 11.32
10.31 12.04
10.14 12.08

Table 24: Cubi SiC energies at high symmetry points, same notation as in Table 21. Average
di eren es between the di erent al ulations of the LDA and GWA band stru tures and the
quasiparti le shifts are 0.19 eV, 0.37 eV, and 0.29 eV, respe tively, and signi antly larger
than the ommonly a epted un ertainty of 0.1 eV in quasiparti le energies. Results of
plane-wave al ulations [42, 130 and of a Gaussian-orbital approa h [114 are ompared.
All energies are given in eV. Comparison with experiment is given in Table 25.

137

Ref.
Expt.a
Aulbur [42
Rohl ng [114
Zhang [121

1v
13.21
12.62 12.46
12.69 12.69

Godby [360
Shirley [43
Aryasetiawan [290

12.85 12.97
X1v
10.86
10.29 10.12
10.37 10.27

Expt.a
Aulbur [42
Rohl ng [114
Zhang [121

15v
0.00
0.00 0.00
0.00 0.00
0.00 0.00
0.34 0.34
0.00 0.00
0.34 0.34

0.00 0.00
X3v
6.81
6.78 6.98
6.79 7.16

Godby [360
Shirley [43
Aryasetiawan [290

10.37 10.50
L1v
11.35
11.01 10.84
11.08 11.02

Expt.a
Aulbur [42
Rohl ng [114
Zhang [121
Godby [360
Shirley [43
Aryasetiawan [290

7.01 6.88
L1v
6.81
6.56 6.74
6.59 6.91

1
1.52
0.47 1.16
0.57 1.32
0.38 1.29

15
4.61
3.80 4.47
3.73 4.60

0.56 1.47

3.70 4.52

0.13 1.02
(1.42)
0.04 1.23
X5v
2.91
2.57 2.68
2.56 2.71
2.71 2.79
2.79 2.87
2.66 2.73
2.73 2.80

Comments
PSP/GO
SO 1st order,
update GF
SO 1st order
w/o (w) ore polarization

3.93 5.61
LMTO
X1
X3
X5
1.90
2.47
1.42 2.00 1.62 2.24 10.19 10.93
1.80 2.65 1.85 2.72 10.33 11.20
1.32 2.05
1.38 2.08 1.55 2.30
1.21 2.07
(1.95)
1.29 2.88 1.59 3.38
L1
L3
1.74
5.45b
0.97 1.62 4.68 5.38
1.13 1.92 4.67 5.65
0.88 1.69

2.72 2.45
L3v
1.41
1.09 1.12
1.10 1.17
1.16 1.19
1.37 1.40
1.07 1.11 1.04 1.82 4.57 5.41
1.28 1.32
0.70 1.55
(1.75)
11.11 11.27 6.84 6.59 1.12 1.01 0.72 2.14 4.66 6.51
Ref. [361 unless noted otherwise, b Ref. [342.

136

10.34 11.50
L1
8.6b
7.74 8.40
8.88 9.92

8.26 9.51

Ref.
Expt.a

1v
12.6, 12.9(2)b

Aulbur [42
Rohl ng [114
Hybertsen [44
Shirley [43

12.74
12.79

X1v
9.3(2)b

Expt.a
Aulbur [42
Rohl ng [114
Hybertsen [44
Shirley [43
Expt.a
Aulbur [42
Rohl ng [114
Hybertsen [44
Shirley [43
a

12.59
12.84
12.86

8.88
8.91

8.87
9.06
9.13

L02v
10.6(5)
10.67 10.60
10.71 10.82
10.89

25v
0.00

2
0.90,0.89

0.00 0.00
0.00 0.00
0.00, 0.30

0.05 0.48
0.01 0.65

X4v
3.15(20),
3.5(2)b
3.02 3.08
3.02 3.16
3.22

L1v
7.7(2)
7.57 7.63
7.63 7.81
7.82

0.71

0.26 0.53
(0.85)
X1
1.3(2)

15
3.25(1),3.006,
3.206
2.59 3.10
2.53 3.21
3.04,3.26

X3

0.70 1.15
1.03 1.74

9.50 10.04
9.54 10.19

0.55 1.28
(1.09)
L03v
1.4(3)
1.37 1.39
1.40 1.47
1.61, 1.43

L1
0.744
0.12 0.61
0.33 0.98

1.23

0.75

0.05 0.70
(0.73)

Comments

update GF, SO 1st order


update GF, w/o (w)
ore polarization

L3
L02
4.3(2),4.2(1)d 7.8(6),7.9(1)d
3.77 4.30
7.07 7.56
3.80 4.57
8.33 9.20
4.33,4.43
7.61

Ref. [182 unless otherwise noted, b Ref. [347, Ref. [359, d Ref. [349.
Table 22: Ge energies at high symmetry points, notation is the same as in Table 21. Both,
GWA valen e- and ondu tion-band energies vary by 0.1 to 1.6 eV between di erent al ulations due to a di erent treatment of ore-valen e polarization and of ore relaxation, a
use of updated quasiparti le energies rather than LDA energies in the Green fun tion, and
di erent degrees of onvergen e (see Table 15). All al ulations use plasmon-pole models.
The hosen basis set is plane waves ex ept for the Gaussian orbital al ulation by Rohl ng
et al. [114. The quasiparti le energies of Hybertsen and Louie [44 and Shirley, Zhu, and
Louie [43 use updated Green fun tions. The data in parentheses in lude ore relaxation and
ore-polarization potentials whi h are ne essary to determine the quasiparti le gap in quantitative agreement with experiment. Hybertsen and Louie in lude spin-orbit (SO) oupling
to rst order. All energies are in eV.

135

Table 21: Comparison of Si LDA (roman), GWA (bold-fa e), and experimental (itali ) energies at the , X , and L point for all quasiparti le al ulations available in the literature.
Quasiparti le energies of di erent al ulations for both ondu tion- and valen e-band states
vary between 0.1 and 0.6 eV due to di erent te hniques, di erent degrees of onvergen e,
et . For ease of omparison, the LDA and GWA valen e band tops are set to zero. The substantial absolute energy shifts of the GWA valen e band maximum with respe t to the LDA
valen e band maximum are given in bra kets in the 025v olumn. Unless noted otherwise,
all al ulations use pseudopotentials (PSP) and plane waves, a plasmon-pole model (PPM),
and determine self-energy shifts in rst-order perturbation theory (PT). Cal ulations that
do not use a plasmon-pole model take the frequen y dependen e of the s reened intera tion
fully into a ount. This frequen y dependen e leads to a valen e-band-width de rease of
about 0.3 eV but a e ts the lowest dire t gaps by only a few tens of a meV. Quasiparti le
energies determined with an updated Green fun tion (GF) { whose energies are given by
the quasiparti le energies obtained in the rst iteration { are given in parentheses. In the
ase of Ref. [102, we give the results of standard GWA and GW (in bra kets) al ulations
(see text). The al ulation of Shirley et al. [353 is not in luded in this table sin e the
GWA values without ore polarization agree with the results of Hybertsen et al. [44 sin e
ore polarization is a small e e t in Si. GO stands for Gaussian orbitals, FLAPW for full
potential linear augmented plane wave. All energies are given in eV.

134

Ref.
Expt.
Aulbur [42
Rohl ng [114
Hamada [285
Hybertsen
[5, 44
Godby [6
Rieger [103
Fleszar [102
Expt.
Aulbur [42
Rohl ng [114
Hamada [285
Hybertsen
[5, 44
Godby [6
Rieger [103
Fleszar [102
Expt.
Aulbur [42
Rohl ng [114
Hamada [285
Hybertsen
[5, 44
Godby [6
Rieger [103

1v

12.5(6),a
11.4,p

25v
0.00

12.4(6)b
11.2q

11.96 11.90
( 12.04)
11.91 11.95
11.95 12.21
11.93 11.84
( 12.04)

11.89 11.57
( 11.58)
11.93 11.57
[ 11.72
X1v
7.82 7.90
( 7.99)
7.77 7.95
7.82 8.11

7.78 7.67
( 7.68)
7.77 7.57
[ 7.68
L02v
9.3(4)a
9.62 9.65
( 9.76)
9.58 9.70
9.63 9.92
( 9.79)
9.57 9.39
( 9.40)
9.58 9.35
[ 9.47

0.65

[
[
[

0.40n
0.31
0.20o

[
[(

[0.07
0:49l
0:53l )

0.63/ 0.06

X4v
2.5(3),a
3.3(2)i
2.87 2.96
( 2.99)
2.78 2.93
2.84 3.03
( 2:99)

2.9,e

2.82/ 2.80
( 2.81)
2.83 2.83
[ 2.88
L1v
6.8(2),a
6.4(4)b
7.00 7.13
( 7.21)
6.94 7.14
6.98 7.31
( 7.18)

15
3.34-3.36,
3.05d
2.56 3.25
(3.30)
2.57 3.36
2.55 3.30
2.57 3.27
(3.35)
2.57 3.30
2.58 3.24
(3.32)
2.55 3.23
[3.22
X1
1.13,g 1.25d

2
4.15(5),e4.1,d
4.21(2)f
3.18 3.86
(3.92)
3.24 3.89
3.17 4.19
(4.08)

0.66 1.31
(1.37)
0.65 1.43
0.65 1.14
(1.44)

9.99 10.72
(10.79)
10.03 10.76

[3.53 4.27m
0.61 1.34
(1.42)
0.65 1.35
[1.34
L03v
1.2(2),e
1.5j
1.21 1.25
( 1.26)
1.17 1.25
1.19 1.26
1.21 1.26
( 1.27)
1.22 1.19
1.17 1.17
( 1.17)
1.19 1.20
[ 1.22

Comments

PSP/GO
FLAPW
update GF

3.56 4.27
3.28 3.94
(4.02)
3.26 3.96
[3.99
X4

2nd order PT
no PPM
update GF
no PPM

10.11 10.54
(10.63)

L1
2.06(3),h
2.40(15)k
1.46 2.13
(2.18)
1.47 2.19
1.43 2.15
1.51 2.18
(2.27)
1.53 2.30
1.46 2.14
(2.22)
1.50 2.18
[2.18

L3
L02
e
3.9(1),
4.15(10)k
3.36 4.13 7.55 8.23
(4.19)
(8.30)
3.32 4.25 7.77 8.56
3.35 4.08
3.37 4.14
(4.24)
3.37 4.11
3.33 4.05 7.71 8.29
(4.14)
(8.39)
3.33 4.06
[4.05

6.96 6.86
( 6.88)
Fleszar [102
6.96 6.78
[ 6.88
133
a Ref. [339, b Ref. [340, Ref. [341, d Ref. [342, e Ref. [343, f Ref. [344, g Ref. [345,
h Ref. [346, i Ref. [347, j Ref. [348, k Ref. [349, l Ref. [311, m Ref. [350, gap at X ,
n estimated from Fig. 1 of Ref. [284, o estimated from Fig. 1 of Ref. [44, p Ref. [351, q
Ref. [352.

132

PSP
TM

LDA
GWA
GWA LDA
GNC
LDA
GWA
GWA LDA

1v
11.98
11.92
0.06
12.07
12.01
0.06

25v
0.00
0.00
0.00
0.00
0.00
0.00

15
2.52
3.19
0.67
2.54
3.21
0.67

2
3.15
3.82
0.67
3.27
4.00
0.73

1
7.64
8.29
0.65
7.70
8.36
0.66

Table 19: Comparison of LDA and GWA energies and the quasiparti le shift at the point
in Si for a Troullier-Martins [325 (TM) and a generalized norm- onserving [326 (GNC)
pseudopotential. Deviations in the GWA band stru ture are largest (0.18 eV) for the 02
state, whi h is the most di ult low-lying ondu tion band state to onverge. The hoi e
of the pseudopotential a e ts the quasiparti le shifts signi antly less than the absolute
energies (60 meV maximum deviation). All numeri al parameters are given in Table 18
ex ept for Gmax whi h equals 3.1 a.u. in the present study. All energies are in eV.

1v
25v
15
0
2
1
0

LH
11.92
0.00
3.19
3.82
8.29

EF
11.82
0.00
3.21
3.81
8.28

X1v
X4v
X1
X4

LH
7.92
2.98
1.26
10.66

EF
7.86
2.96
1.30
10.60

L02v
L1v
L03v
L1
L 3
L02

LH
9.67
7.15
1.26
2.08
4.08
8.17

EF
9.59
7.07
1.25
2.10
4.10
8.18

Table 20: Comparison of quasiparti le energies al ulated with the von der Linden{Hors h
[122 (LH) and the Engel{Farid [120 (EF) plasmon-pole models for high-symmetry points
in Si. The typi al deviation between the two sets of quasiparti le energies lose to the band
gap is on the order of a few tens of a meV. The largest dis repan y of 0.10 eV o urs for the
low-lying 1v state, for whi h the plasmon-pole model is an insu ient approximation. All
al ulational details are identi al to those given in Table 18 ex ept for Gmax whi h equals
3.1 a.u. in the present study. Minor di eren es with the LH Si band stru ture energies in
Table 21 result from a better onvergen e in the latter. All energies are in eV.

131

n(r)

Nkpt
E ut
P 0 Nkpt
E ut
Gmax
N b
 Nkpt
E ut
Gmax
Nppm
N b

Si
10
8.5
10
8.5
3.4
146
10
8.5
3.0
60
60

Ge GaAs SiC GaN


28
28
10 10
10
10
25 25
10
10
10 10
10
10
25 25
3.4 3.1 4.5 4.5
146 146 146 196
28
10
10 10
10
10
25 25
3.0 3.0 4.5 4.5
60
60 100 80
100 100 150 150

Table 18: Parameters used to determine the self- onsistent density n(r), the independentparti le polarizability P 0 [ f. Eq. (116), and the self-energy  [ f. Eqs. (117) and (118)
for Si, Ge, GaAs, SiC, and GaN. All wave fun tion omponents are kept in the al ulation.
The von der Linden{Hors h plasmon-pole model and the Gygi{Balderes hi s heme for the
integration of the Coulomb singularity are used. For the latter s heme, the plasmon-pole
band stru ture is determined at q = 0:00125qX using the equivalent of 60 spe ial k-points
in the irredu ible Brillouin zone. Troullier{Martins pseudopotentials with non-linear ore
orre tions for GaAs and GaN are used to model the ioni potential. The energy ut-o
E ut is in Hartree, the ut-o value Gmax for sums over re ipro al latti e ve tors is in atomi
units. N b equals the number of uno upied bands for P 0 and the number of o upied and
uno upied bands for . Nkpt is the equivalent number of k-points in the irredu ible Brillouin
zone obtained using the full spa e-group symmetry of the rystal and Nppm is the number of
plasmon-pole bands kept. All al ulations are done at the experimental latti e onstant.

130

E ut
8.5
12.0
18.0

0
0
0
1v
1
25v 15
2
11.90 0.00 3.25 3.86 8.32
11.88 0.00 3.17 3.80 8.26
11.88 0.00 3.23 3.83 8.33

Table 17: Convergen e of valen e and ondu tion band energies at the point in Si as a
fun tion of the energy ut-o used to determine the self- onsistent ground-state density as
well as the wave fun tions used to al ulate the independent-parti le polarizability and the
expe tation values of the self-energy operator. Deviations between the di erent eigenvalues
are less than 0.08 eV. All al ulational parameters are given in Table 18 ex ept for the ut-o
in re ipro al spa e for the determination of  whi h is 2.7 a.u. for the present study. The
ut-o energy E ut is given in Hartree.

129

d ele trons Co iorva


Chang
ore
1.72
1.65 (1.93)
NLCC

1.60

valen e

0.84

Exp.a
a

Egap (eV)
Zakharov

Rohl ng Fleszar
2.15 3.70 2.18 3.83

1.36 2.79
0.3 (0.67)

0.78 1.50
2.50/2.55b

alat (
A)
Co iorva Rohl ng
5.05
5.05
( 13.2%) ( 13.2%)
5.33
( 8.4%)
5.78
5.61
( 0.7%) ( 3.6%)
5.818

Ref. [299 unless noted otherwise, b Ref. [300.

Table 16: LDA and GWA (bold fa e) energy gaps and LDA latti e onstants (per ent deviation from experiment in parentheses) in omparison with experiment for ubi CdS. Co iorva et al. [196 use s alar-relativisti Troullier-Martins pseudopotentials in the KleinmanBylander form (E ut = 25 Hartree for d ele trons in ore, 45 Hartree for d ele trons in
valen e). Chang et al. [301 use s alar-relativisti Ba helet-Hamann-S hluter pseudopotentials (E ut = 6.75 Hartree for d ele trons in ore, 9.5 Hartree for d ele trons in valen e) and
show that the negle t of relativisti e e ts (numbers in parentheses) in reases fundamental
band gaps by about 0.3 eV. Zakharov et al. [51 use semirelativisti , non-lo al pseudopotentials with non-linear ore orre tions (NLCC) [205 (E ut = 12.5 Hartree). Rohl ng et
al. [52 and Fleszar [302 use s alar-relativisti Ba helet-Hamann-S hluter pseudopotentials.
The di eren e of about 0.5 eV in the fundamental LDA band gap between di erent Cd2+
al ulations is of the same order as the GWA band-gap in rease upon in lusion of 4s and 4p
ele trons as valen e ele trons in GWA al ulations. In lusion of the 4d ele trons as valen e
ele trons leads to a reprodu tion of the experimental latti e onstant to within 3.6% [52
and 0.7% [196. This di eren e in the equilibrium stru ture leads to di eren es in the
fundamental band gap of 0.2 to 0.3 eV [196, 303. The LDA and GWA energy gaps are
determined at the experimental latti e onstant in all al ulations.

128

X1
L1
L02
GaAs 1
X1
X3
L1
L1

Ge

PW
LDA GW
0.70 1.15
0.12 0.61
7.07 7.56
0.47 1.16
1.42 2.00
1.62 2.24
0.97 1.62
7.74 8.40

60 GO
LDA GW
0.79 1.36
0.18 0.76
7.46 8.11
0.52 1.21
1.47 2.14
1.66 2.37
0.98 1.66
8.08 8.86

40 GO
LDA GW
1.03 1.74
0.33 0.98
8.33 9.20
0.57 1.32
1.80 2.65
1.85 2.72
1.13 1.92
8.88 9.92

Table 15: Convergen e of LDA and quasiparti le energies for sele ted states in Ge and
GaAs for a Gaussian-orbital-based method [114, 295 in omparison to a plane-wave (PW)
al ulation [42. For both materials at least 60 Gaussian orbitals (GO) are ne essary to
obtain a onverged LDA band stru ture. The GWA band stru ture may require more than
60 Gaussians for omplete onvergen e. A 40-Gaussian basis set is used in the literature [114
but that set is insu ient to obtain band stru tures that are a urate to within 0.1 eV for
small- and medium-gap semi ondu tors. Note that improving onvergen e of the Gaussianorbital al ulation moves the results systemati ally towards the plane wave results. All
energies are in eV.

127

Method
self-energy/s reening
LDA
GWA/RPA
GWA/RPA+V+SC
GWA+V+SC/RPA
GWA+V+SC/RPA+V+SC
Expt.a;b
a Ref. [182, b Ref. [274.

2.5
3.3
3.4
3.6
3.7
3.4

Si
X
3.4
4.2
4.3
4.5
4.6
4.3

L
2.6
3.4
3.4
3.7
3.8
3.5

diamond
5.5
7.6
7.8
8.1
8.4
7.3

Table 14: In uen e of lowest-order vertex (V) and self- onsisten y (SC) orre tions to the
self-energy (GWA vs. GWA+V+SC) and to the diele tri s reening (RPA vs. RPA+V+SC)
on the fundamental band gaps at , X , and L in Si and at in diamond. Lowest-order
orre tions to the diele tri s reening lead to a small in rease in fundamental band gaps (
0.1 eV in Si,  0.2 eV in diamond). Lowest-order orre tions to the self-energy lead to a
substantial in rease in the fundamental band gap ( 0.3 eV in Si,  0.5 eV in diamond)
resulting in a dis repan y of about 0.3 eV in Si and 1 eV in diamond between al ulation and
experiment. Within the approximations of the al ulation (LDA Green fun tion, plasmonpole model, et .) the e e ts of vertex and self- onsisten y orre tions do not an el. Energies
are in eV. Table adopted from Ref. [119.

126

GWRPA GWKx GW
Dire t gap at
0.64
0.56
0.65
Dire t gap at X
0.78
0.57
0.73
Dire t gap at L
0.68
0.58
0.72
Valen e bandwidth
0.56
1.01
0.48
Minimum gap
0.63
0.59
0.66
Valen e band maximum 0.36
0.44
0.01
Table 12: Quasiparti le orre tions (GWA minus LDA energy values in eV) for Si al ulated within GWRPA (no vertex orre tions for the diele tri matrix " and self-energy ),
GWKx (vertex orre tions only in " but not in ), and GW (vertex orre tions in " and
; orre tions listed in rst ve rows, LDA gap = 0.52 eV). The last row is an absolute
quasiparti le orre tion to the valen e band maximum. LDA vertex orre tions in the polarizability redu e fundamental band gaps by about 0.1 eV to 0.2 eV and the valen e band
width by about 0.5 eV. Taking vertex orre tions into a ount for both the polarizability
and the self-energy does not have a signi ant e e t on relative energy di eren es ompared
to RPA-based GWA but shifts the absolute energy s ale by about 0.4 eV. Table adopted
from Ref. [89.

rs
2
3
4
5

Z (0); Z (kF )
0.6,0.8
(0.6,0.8)
0.5,0.7
(0.6,0.7)
0.5,0.6
(0.6,0.7)
0.4,0.6
(0.5,0.7)

GWA
Higher order
w
EF
Z (0); Z (kF ) w
11.9
0.10
0.5,0.8
11.6
(13.3) (0.13)
5.0
0.05
0.5,0.7
5.0
(6.0) ( 0.04)
2.6
0.09
0.5,0.6
2.7
(3.3) ( 0.08)
1.6
0.10
0.4,0.6
1.7
(2.3) ( 0.08)

EF
0.08

Exa t
EF
0.10

0.06

0.04

0.09

0.08

0.09

0.08

Table 13: Quasiparti le weight of jellium at k = 0 and k = kF (kF = Fermi wave ve tor), band
width w, and Fermi energy EF for a non-self- onsistent GWA al ulation, a partially self onsistent GW0 A al ulation (data in parentheses), and a GW0 A al ulation that in ludes
dynami vertex orre tions to se ond order in W in the self-energy (data under \Higher
order") evaluated at several values of rs . Exa t values for EF are given as well. The
s reened intera tion ontains a stati vertex orre tion. Self- onsisten y improves EF ex ept
for rs = 2 where the plasmon-pole model of Ref. [232 is only marginally valid but in reases
Z and w in ontradi tion to experiments on simple metals. Dynami vertex orre tions
almost ompletely an el self- onsisten y e e ts. Table adopted from Ref. [232.
125

LDA
Cd 4d
Ge 3d
Si 2p

7.2
6.8a
24.6
24.4
89.4

GWA
GQP S
9.1
9:7a;b
27.7
30.0

28.5
30.1 ;d
94.8
100.4

GLDA
8.1

Expt.
9.2,e 9.5f
29.5,g 29.7h
99.0,g 100.0h

Ref. [218; b SIRC-PSP; Ref. [145; d STS; e Ref. [219; f Refs. [220, 221; g Ref. [222; h
Ref. [223.
Table 11: Cal ulated binding energies in eV of the semi ore states Cd 4d in ubi CdS, Ge
3d in Ge, and Si 2p in Si. The zero of the energy s ale is given by the respe tive valen e-band
maximum. The experimental data are weighted averages of spin-orbit-split levels and are
taken as quoted in Ref. [213. The symbols GLDA and GQP S orrespond to GWA al ulations
using an LDA propagator or a propagator al ulated with a renormalized spe tral fun tion
(approximately self- onsistent GWA al ulation, see Ref. [213). All values are taken from
Ref. [213 with the following ex eptions: In the ase of Ge we also list LDA, GLDAWA,
and Slater-transition-state (STS) results obtained by an LMTO al ulation [145. For CdS,
we list the LDA and self-intera tion- and relaxation- orre ted pseudopotential (SIRC-PSP)
results of Ref. [218.

124

Quantity

LDA

Ge
8v ! 7
8v ! X5
8v ! L6
L6 ! X5
GaAs
8v ! 6
8v ! X6
8v ! L6
L6 ! X6
X6 ! X7
a Ref. [208, unless noted otherwise; b Ref. [209.

QP
QP Expt.a
CVI in CVI in
LDA
CPP

0.26

0.53

0.55 1.28
0.05 0.70
0.60 0.58

0.85
1.09
0.73
0.36

0.89
1.10b
0.744
0.36

0.13

1.02

1.42

1.52

1.21
0.70
0.51
0.21

2.07
1.56
0.52
0.26

1.95
1.75
0.20
0.33

2.01
1.84
0.17
0.40

Table 10: Band energy di eren es in Ge and GaAs in eV. Results for LDA full-potential al ulations, quasiparti le (QP) al ulations with an LDA treatment of ore-valen e intera tions
(CVI), quasiparti le al ulations with a ore-polarization-potential-based (CPP) treatment
of ore-valen e intera tions, and experiment are shown. All results in lude ore-relaxation
e e ts (added a posteriori for the quasiparti le al ulations). Fundamental band gaps in the
di erent approa hes are printed in bold fa e. Overall agreement between experiment and
quasiparti le al ulations is improved upon in lusion of ore-polarization e e ts. In parti ular, Ge is predi ted to be an indire t rather than a dire t gap semi ondu tor. Table adapted
from Ref. [43.

123

material

k-point

Si

X
L

Ge

X
L

GaAs

X
L

VBM
0.79
0.78
0.78
0.79
0.77
0.78
0.79
0.78
0.79

CBM
0.79
0.80
0.80
0.79
0.80
0.80
0.80
0.81
0.81

material

k-point

SiC

X
L

GaN

X
L

C
LiCl

VBM
0.82
0.82
0.82
0.82
0.83
0.82
0.86
0.83

CBM
0.82
0.85
0.83
0.85
0.87
0.86
0.86
0.87

Table 9: Quasiparti le weight Zi (Eq. (18)) for the valen e band maximum (VBM) and the
ondu tion band minimum (CBM) at , X , and L for Si, Ge, GaAs, SiC, GaN, diamond,
and LiCl. Zi for the VBM and CBM of diamond and LiCl is taken from Ref. [44, all
other values are from Ref. [42. For the sp-bonded materials shown in the table, Zi is equal
to 0.8 to within 10% and therefore approximately a material- and state-independent onstant. Note, however, that ovalently-bonded semi ondu tors, whi h have larger diele tri
onstants, show a stronger dynami renormalization than ioni insulators.

122

Si
COH
0
25v
X1
SEX
0
25v
X1

COHSEX
no LF
LF

GWA

8.72
8.72

10.30
8.70

8.41
7.40

4.44
2.37

3.85
2.08

3.56
1.65

Table 7: The stati COH and SEX ontributions to the valen e-band-maximum and
ondu tion-band-minimum self-energies with and without lo al elds for Si in omparison
to the GWA self-energy. Lo al- eld e e ts a e t o upied states signi antly and lead to an
about 1.6 eV de rease in COH for 025v whereas SEX is less sensitive to lo al elds (0.6 eV
for 025v , 0.3 eV for X1 ). Dynami orre tions shift the ondu tion and valen e self-energies
upwards by about 10 to 20%. In absolute terms and for the total self-energy, the dynami
orre tion is larger for the valen e bands and leads to a band gap de rease. Table adapted
from Ref. [44.
Material Site
Si
BC
I
GaAs
BC
I
AlAs
BC
I
C
BC
I

rnlo in jellium (a.u.)


rnlo (a.u.) n(rs )
n(r)
4.1
3.9
2.8
4.7
3.9
8.8
4.2
4.0
2.8
4.3
4.0
9.0
4.3
4.0
2.8
4.6
4.0
9.0
2.8
2.7
2.2
3.5
2.7
4.7

Table 8: Range rnlo of the self-energy nonlo ality evaluated at a bond- entered (BC) and
an interstitial (I) site in Si, GaAs, AlAs, and diamond ompared to the orresponding value
of the jellium self-energy evaluated at the Fermi energy and at (i) the average density of
the semi ondu tor n(rs ), and (ii) the lo al density n(r) at a point r in the semi ondu tor.
rnlo equals the spheri ally averaged distan e to the rst zero in the os illatory fun tion
(r; r0 ; E = midgap) with r xed at a BC or I site. The self-energy of jellium at the
average density of the semi ondu tor underestimates the radius rnlo of the full al ulation
on average by about 10%. The \lo al density" jellium al ulations severely underestimate
(overestimate) rnlo in high (low) density regions ( 30% on average for a BC site, +80% on
average for an I site). Table adapted from Ref. [185.
121

(1,1,1)
(2,2,0)
(3,1,1)
(2,2,2)
(4,0,0)

Hartree
1.42
0.14
0.30
0.20
0.34

LDA COHSEX Hartree-Fo k


1.67 1.59
1.77
0.13 0.14
0.16
0.36 0.35
0.42
0.31 0.29
0.43
0.40 0.38
0.43

Table 5: Sele ted Fourier oe ients of the valen e density in Si obtained by Hartree, LDA,
diagonal COHSEX (stati , no lo al elds), and Hartree-Fo k al ulations using the single
mean-value point te hnique. All values are given in ele trons per unit ell. The degree of
density lo alization is lowest in the Hartree and highest in the Hartree-Fo k al ulation. The
LDA density lies between these two extremes and is losest to the density obtained from a
self- onsistent COHSEX al ulation. Table is adapted from Ref. [90.

LDA COHSEX COHSEX


no LF
LF
diamond 3.9
5.1
6.6
Si
0.52
0.50
1.70
Ge
0.07
0.33
1.09
LiCl
6.0
8.2
10.4
a Ref. [182 unless otherwise noted, b

GWA Expt.a
5.6 5.48
1.29 1.17
0.75 0.744
9.1 9.4b
Ref. [183.

Table 6: Dire t and indire t band gaps for the ovalently bonded semi ondu tors Si and
Ge and for the insulators diamond and LiCl using LDA, the stati COHSEX approximation
with and without lo al elds (LF), and the GWA in omparison with experiment. The LDA
band gap underestimates experiment by at least 0.7 to 3.4 eV. The COHSEX approximation
without lo al elds leads (with the ex eption of Si) to an in rease in the fundamental band
gap but still underestimates the experimental values. The in lusion of lo al elds leads to a
further band-gap in rease and to an overestimation of experiment by about 0.4 to 1.1 eV.
Dynami e e ts (GWA) redu e this overestimation and reprodu e experiment to within 0.1
to 0.3 eV. Note, that relativisti e e ts and ore ele trons an have a large in uen e on
semi ondu tor gaps as shown in Table 33. This table is taken from Ref. [44.

120

feature

ore

H^ 0

basis

dire t gap (eV)


th =E exp (material, exp. diele tri onstant)
Egap
gap
Liparia
HF
HF MB/OPW
13.7/14.3 (Ar,1.67)
7.5/7.1-7.4 (NaBr,2.60)
8.61/8.75 (NaCl,2.33)
Kanea
EPSP
EPSP
PW
N/A
Brenera
valen e
HF
LCAO
7.6/7.3-7.6 (C,5.70)
17.9/13.6 (LiF,1.96)
Baronia
valen e
HF GO+OPW
5.24/4.99 (LiH,3.61)
14.62/14.15 (Ar,1.67)
a
Gygi
LDA/PSP LDA PSP/PW
3.24/3.4 (Si,11.7)
Hybertsenb LDA/PSP LDA PSP/PW
3.3/3.4 (Si,11.7)
b
Godby
LDA/PSP LDA PSP/PW
3.27/3.4 (Si,11.7)
a stati COHSEX al ulation negle ting lo al elds and based on a model diele tri fun tion;
b GWA al ulation in luding energy dependen e (plasmon-pole model in Ref. [5) and lo al
elds and based on rst-prin iples diele tri matrix.
Table 4: Comparison of te hni al aspe ts of COHSEX al ulations by Lipari et al.
[133, 134, 135, 136, Kane [137, Brener [138, 139, Baroni et al. [140, 141, and Gygi and
Balderes hi [90 with GWA al ulations by Hybertsen and Louie [5 and Godby, S hluter, and
Sham [6. Core ele trons are either treated on an LDA-pseudopotential (PSP) or HartreeFo k (HF, negle t of ore-valen e polarization) level or treated on the same level as the valen e ele trons. Most COHSEX al ulations start from a Hartree-Fo k independent-parti le
Hamiltonian H^ 0 , whi h is appropriate onsidering the small diele tri onstants of the materials. GWA al ulations use LDA as an independent-parti le Hamiltonian instead. Agreement
with experiment for the dire t band gap is in general within a few tenths of an eV. Values for
the band gap and the diele tri onstant are taken from the original papers with the ex eption of the diele tri onstant of LiF [142 and NaBr and NaCl [143. Other abbreviations
that are used in the above table are EPSP = empiri al PSP, MB = mixed basis, (O)PW =
(orthogonalized) plane wave, GO = Gaussian orbital, LCAO = linear ombination of atomi
orbitals.

119

!0 (0)

Si
Ge

Theorya

Expt.b
16.7

Theorya

15.7 (15.9)
0.36 (0.34)
14.2
15.9 - 16.5 0.38 [100, 0.35 [111,
0.25 [110
GaAs
14.1
15.7
0.49

Expt.b
0.41
0.38d
0.44,e 0.61 [100,
0.57 [110, 0.53 [111f

SiC
22.5 (22.4)
22.1
GaN
19.4
a Ref. [42 ex ept for values in parentheses, b Ref. [124 for ! (0) and Ref. [125 for unless
0
otherwise noted, Ref. [126, d Ref. [127, e Ref. [128, f Ref. [129.
Table 3: Theoreti al and experimental plasmon energies and dispersion oe ients for Si,
Ge, GaAs, SiC, and GaN. The theoreti al values of Engel and Farid for Si [120 and Ba kes
et al. for SiC [130 are listed in parentheses. Agreement between the di erent al ulations
is within a few per ent. The theoreti al and experimental plasmon energies agree to within
10% and the dispersion oe ients to within 30%.

118

i (r) i (r0 ) Z A(r; r0 ; E 0 ) 0


 C E E 0 dE
E Ei
i
X  (r) (r0 )
i
i
Independent-parti le Green fun tion [Eq. (15): G0 (r; r0 ; E ) =
E
"i
i
ZZ
0
0
0
0
Dyson's equation [Eq. (16): G(r; r ; E ) = G (r; r ; E ) + G (r; r1; E )(r1; r2 ; E )G(r2; r0 ; E )dr1dr2
Z
1
Quasiparti le equation [Eq. (3): [ r2 + VH + Vext i (r) + (r; r0 ; Ei ) i (r0 )dr0 = Ei i (r)
2
First-order perturbation theory for Ei [Eq.2(17):
Ei 3"i + Zi hi j("i ) Vx ji i

1



(
E
)
i

5
Quasiparti le weight Zi [Eq. (18): Zi = 41

E E ="
Dynami ally s reened intera tion approximation (GWA) [Eqs. (22)-(24):
(1; 2; 3) = (1; 3) (2R ; 3) (1; 2) = iG(1; 2)W (1+; 2) P (1; 2) = iG(1; 2)G(2; 1)
W (1; 2) = v (1; 2) + W (1; 3)P (3; 4)v (4; 2)d(3; 4)
Independent-parti le polarizability [Eq. (32):
!
X
fi (1 fi )
fi (1 fi )


0
0
0
0
P (r; r ; ! ) = i (r)i (r)i (r )i (r )
+
"i "i + ! + i "i "i ! + i
i;i
4
0
A
Diele tri matrix in RPA [Eq. (34): "RP
GG (q; ! ) = GG
jq + Gj2 PGG (q; !)
4
1
Dynami ally s reened intera tion [Eq. (27): WGG (q; ! ) =
jq + Gj2 "GG (q; !)
Energy-dependent orrelation ontribution to the self-energy [Eq. (36):
o X V (r)V  (r0 ) (r) (r0 ) uno
X
X X V (r)V  (r0 ) (r) (r0 )
m
i
m
i
m
i
m
i
C (r; r0; E ) =
+
E + "m "i i
E "m "i + i
i m6=0
i m6=0
Stati Coulomb hole self-energy [Eq. (43): COH (r; r0 ) = 21 (r r0 )[W (r; r0; E = 0) v (r; r0)
o
X
i (r)i (r0 )W (r; r0; E = 0)
Stati s reened ex hange self-energy [Eq. (44): SEX (r; r0 ) =
Intera ting Green fun tion [Eq. (13): G(r; r0; E ) =

Table 2: Important equations for the GWA. Equation numbers within square bra kets equal
those in the text.

117

Symbol
1 = (r1 t1 )
; EF
^ r) or
^ y (r)
(
i, nk
"i
EN;i
Ei = EN +1;i EN;0 ; Ei  
Ei = EN;0 EN 1;i ; Ei < 
i (r) or nk (r)
jN; ii
^ r)jN + 1; ii; Ei  
i (r) = hN; 0j (
^ r)jN; 0i; Ei < 
i (r) = hN 1; ij (
0
G(1; 2) or G(r; r ; E )
A(r; r0 ; E ) = 1= jImG(r; r0 ; E )j
v (1; 2) = (t1 t2 )=jr1 r2 j
^ y(rt) (
^ rt)jN; 0i
n(rt) = hN; 0j
^ y(rt) (
^ rt) n(rt)
n^ 0 (rt) =
R
VH (1) = n(2)v (1; 2)d2
Vext (1)
V (1) = VH (1) + Vext(1)
P (1; 2) = n(1)=V (2)
(1; 2) = n(1)=VRext(2)
"(1; 2) = (1
; 2)
v (1; 3)P (3; 2)d3
R
W (1; 2) = " 1 (1; 3)v (3; 2)d3
(r; r0 ; E )
= X (r; r0) + C (r; r0; E )
= COH (r; r0 ; E ) + SEX (r; r0 ; E )
(1; 2; 3) R= G 1 (12)=V (3)
Vm (r) = v (r; r0 )hN; mjn^ 0 (r0 )jN; 0idr0
"m = EN;m EN;0

De nition
(spatial time) oordinate of rst parti le
hemi al potential, Fermi energy
Fermion annihilation or reation operator
quantum number, band index n and wave ve tor k for solids
single-parti le energy
N -ele tron total energy for state i
ith quasiparti le energy
ith quasihole energy
wave fun tion of single-parti le Hamiltonian
ith ex ited (i=0 ground) state of N -ele tron system
quasiparti le many-body amplitude
quasihole many-body amplitude
single-parti le Green fun tion
spe tral fun tion
bare Coulomb intera tion
ele tron density
density u tuation operator
Hartree potential
external perturbation potential
total potential
irredu ible polarizability
full polarizability
diele tri matrix
dynami ally s reened intera tion
non-Hermitian, non-lo al, energy-dependent self-energy
= ex hange + energy-dependent orrelation self-energy
= Coulomb hole + s reened ex hange self-energy
vertex fun tion
u tuation potential
energy of ele tron-hole ex itation

Table 1: De nitions of symbols and quantities used throughout this arti le.

116

For latti e onstants, both LDA and GGA give about 1% errors, but LDA gives too small
values while GGA gives too large value [555, 673.

115

In the intera ting system the fun tional F [n0 is equal to the sum of the kineti energy,
the Hartree energy, and the Coulomb energy of the ex hange- orrelation hole g , while the
Kohn-Sham system is des ribed by the kineti energy T0 [n0 , the Hartree energy, and the
Coulomb energy of the averaged ex hange- orrelation hole g~. Hen e, the e e t of the oupling onstant average is to in orporate the di eren e between T0 and the total physi al
kineti energy into the Kohn-Sham ex hange- orrelation fun tional Ex . The Kohn-Sham
onstru tion is made spe i ally to obtain a set of single-parti le equations by whi h the
exa t density an be found. However, the partitioning of F [n into a sum of T0 [n, EH [n,
and a remainder Ex [n is not a physi al partitioning and the ex hange- orrelation energy
therefore ontains both kineti and ex hange- orrelation energy.
f. Lo al approximations
For pra ti al implementations of the Kohn-Sham s heme, an approximation must be hosen
for the ex hange- orrelation energy Ex [n or the ex hange- orrelation potential Ex [n=n.
The most ommonly used approximation is the lo al density approximation (LDA) [33, in
whi h the lo al ex hange- orrelation energy per ele tron is approximated by the ex hange orrelation energy per ele tron of an homogeneous ele tron gas with the lo al density. In
general, we an de ne an ex hange- orrelation energy per ele tron Ux (r) by:

Ex [n =

n(r)Ux (r) dr:

(188)

In LDA, it is assumed that U is a fun tion (N.B. not `fun tional') of the lo al density,
that is, ULDA (r) = ULDA (n(r)). There are several parametrizations, for example, Refs.
[664, 665, for ULDA (n) based on a urate al ulations for the homogeneous ele tron gas
[355. Histori ally, Slater's density fun tional theory [666 based on lo al ex hange pre eded
the formal foundation in Kohn-Sham theory. Even earlier, the rst de fa to density fun tional
theory was the Thomas-Fermi equation in whi h the kineti energy is also treated in a lo al
approximation [667, 668.
The lo al-density approximation is by onstru tion exa t for homogeneous systems, and
is the zeroth-order term in an expansion of Ex [n in terms of the spatial gradients of n. Attempts to in lude more terms in the gradient expansion turned out to be di ult. A straightforward gradient expansion (GEA) [33 yields a g~ that violates the ex hange- orrelation-hole
sum rule, whi h leads to severe problems [669, 670. More sophisti ated so- alled generalized
gradient approximations (GGA) [669, 670, 671, 672 assume that U is a fun tion of the density and its gradients rn, that is, UGGA (r) = UGGA (n(r); rn(r)), but without limiting UGGA
to be an a tual gradient expansion of U (r). Instead, the various GGA ex hange- orrelation
energies that have been proposed are spe i ally onstru ted to obey the important sum
rule for g~ and several other exa t relations that it has been shown that a good U (r) should
ful ll. However, although GGA often yields better results than LDA, for example, for atomi
total energies and ohesive energies in rystals, there are several ases in whi h GGA gives
worse results than LDA, for example, for bulk moduli and phonon frequen ies [555, 673.
114

orrelation among ele trons with opposite spin.


e. Coupling- onstant averages
A formal relationship between the physi al, intera ting ele tron system and the nonintera ting Kohn-Sham system an be obtained by a oupling- onstant integration in whi h the
ele tron-ele tron intera tion is multiplied by a parameter  that is varied between 0 and 1
[37. In addition { and this additional onstraint is what makes the pro edure useful { we
require that the ele tron density should be the same for all , whi h is a hieved by introdu ing a titious single-parti le potential V (r) [663. The  dependen e of V (r) is impli itly
given by the requirement that n (r) = n0 (r) for all .
The Hamiltonian H^  for a given  is:
N
N
N
X
X
1 2 X

H^  =
(181)
r
+ V (ri ):
+
i
i=1 2
i<j jri rj j i=1
By onstru tion, we must re over the intera ting system for =1 and the Kohn-Sham system
for =0, whi h implies:
V=1 = Vext ; V=0 = VKS :
(182)
Denoting the ground-state wave fun tion for a given  by  , the total ground-state energy
E is
Z
E = h  jT^j  i + h  jV^Coul j  i + V (r)n0 (r) dr:
(183)
V

From the Hellmann-Feynman theorem, dE =d = h  jdH=dj i, we have


Z
dV (r)
dE
= h  jV^Coul j  i +
n0 (r) dr;
(184)
d
V d
whi h after integration over  from 0 to 1 together with the relations in Eq. (182) yields
Z 1
Z
(185)
E=1 = E=0 + h  jV^Coul j  i d + [(Vext (r) VKS (r) n0 (r) dr:
V
0
R
R
But E=0 =T0 [n0 + V VKS (r)n0 (r) dr and E=1 =F [n0 + V Vext(r)n0 (r) dr, so the singleparti le potentials an be eliminated from Eq. (185), and we obtain a relation between the
universal fun tionals F [n0 and T0 [n0 at the ground-state density n0 :
#
"
Z 1
1 Z 1 Z n0 (r)n0 (r0 )g (r; r0 )
0
^
drdr d:
F [n0 = T0 [n0 + h  jVCoul j  i d = T0 [n0 +EH [n0 +
2 0 V
jr r0j
0
(186)
R
We now de ne the average ex hange- orrelation hole g~ = 01 g d and rea h the important
on lusion that the ex hange- orrelation energy Ex in Kohn-Sham theory is equal to the
Coulomb energy of the oupling- onstant averaged pair-distribution fun tion:
1 Z n0 (r)n0 (r0 )~g(r; r0)
Ex [n0 =
drdr0:
(187)
2 V
jr r0j
113

That is, if one ele tron is taken to be at r the total number of remaining ele trons in all of
spa e is exa tly N 1 not N . The sum rule for g subtra ts out this one ele tron from the
density distribution n(r0 )(1 + g (r; r0)) as a fun tion of r0 for xed r.
Though the sum rule prevents g from being zero in all of spa e, g typi ally approa hes
zero when r and r0 are far apart, whi h means that the ele trons are un orrelated at large
distan es. The ex hange- orrelation hole is therefore often of nite extent, and for a given
ele tron in r it des ribes the redistribution of the other ele trons in the vi inity of r due to
ex hange and Coulomb repulsion. See, for example, Ref. [648 for a Monte Carlo al ulation
of the ex hange- orrelation hole in sili on, whi h arti le also onsiders the oupling- onstant
dependen e dis ussed in the next se tion.
For ele trons with spin 1=2, ea h spatial oordinate is asso iated with a spin index whi h
has two values (1=2) or `"' and `#'. The density then has two non-zero omponents and
the pair-distribution fun tion is a two-by-two matrix in the spin indi es. The sum rule in
Eq. (177) is then modi ed to
Z

n" (r0 )g "" (r; r0) dr0 = 1;

(178)

n" (r0 )g "# (r; r0 ) dr0 = 0;

(179)

and the sum rules for the other two g omponents are obtained by inter hange of " and # in
Eqs. (178) and (179).
These two relations an be understood by extending the motivation for the sum rule
for spinless parti les to fermions with N " and N # parti les of ea h spin respe tively. If the
parti le in r is assumed to have spin up, there are N " 1 more parti les with spin up in the
distribution des ribed by n" (r0 )(1 + g "" (r; r0 )), whi h gives Eq. (178). However, there are
still N # parti les of opposite spin left in the distribution n" (r0 )(1 + g "# (r; r0 )), whi h gives
Eq. (179).
The pair-distribution fun tion plays a unique rule in an intera ting ele tron system be ause the exa t Coulomb energy of the system is equal to the Coulomb energy of the distribution n(r; r0 ):

h jV^Coulj i = 21

n(r; r0)

V r

Z
0
0
0 = 1 n(r)n(r )[1 + g (r; r ) drdr0:
d
r
d
r
r0 j
2 V
jr r0j

(180)

From this equation we see dire tly that g = 0 gives the Hartree energy, while the ex hange
and orrelation e e ts are des ribed by g . For a system of nonintera ting ele trons des ribed
by a single Slater determinant there are no orrelation e e ts only ex hange. The sum rule
for g des ribes the important role of ex hange to subtra t out the self-intera tion pie e from
the Hartree term, whi h pie e has been unphysi ally in luded in the Hartree term when
de ned in terms of an integral over the total densities. For spin one-half ele trons g "" des ribes both ex hange and Coulomb orrelation among the equal-spin ele trons, and the sum
role for g "" ensures that the self intera tion is subtra ted out, while g "# des ribes Coulomb
112

onstant x . Note that sin e the potential only hanges by a onstant, there is no di eren e
between the Kohn-Sham wave fun tions in the (N +1)-ele tron system and the N -ele tron
system.
The dis ontinuity x originates solely from the ex hange- orrelation potential. The
external potential is by onstru tion un hanged, the Hartree potential has a simple, dire t
dependen e on the density, whi h only hanges in nitesimally, while the dis ontinuity in the
kineti energy T0 is exa tly equal to the Kohn-Sham gap "N;N +1 "N;N . This dis ontinuity
in the kineti energy is due to the qualitative di eren e between the lowest ondu tionband orbital and the highest valen e-band orbital. However, the de nition of the kineti
energy in terms of the squared gradient of the orbital means that, sin e the orbitals in the
(N +1)-ele tron system and the N -ele tron system are the same, the dis ontinuity in the
kineti energy is the same whether we al ulate it with the orbitals in the N -ele tron system
or from the lowest ondu tion-band orbital in the (N +1)-ele tron system and the highest
valen e-band orbital in the N -ele tron system [662.
Numeri al implementations of Kohn-Sham theory, using LDA or GGA (see Se tion f.
of this appendix), typi ally obtain Kohn-Sham band gaps about 0.5{2 eV smaller than the
experimental gaps, see Fig. 3, Se tion 3. Even though some of this dis repan y an be
due to the LDA or GGA approximations, there is eviden e that a signi ant part is due to
x [6. This inability of Kohn-Sham theory to give band gaps lose to experiment is often
refered to as the `band-gap problem' and is the main reason why quasiparti le al ulations
are needed as a omplement to Kohn-Sham theory when uno upied bands are onsidered.
d. The ex hange- orrelation hole
In terms of a normalized N -ele tron wave fun tion (r1 ; r2 ; : : : ; rN ), we de ne the density
n(r) by
Z
(174)
n(r) = N j (r; r2; : : : ; rN )j2 dr2 : : : drN :
V

Similarly, we an de ne a pair-distribution fun tion n(r; r0) by


Z
n(r; r0) = N (N 1) j (r; r0; r3 ; : : : ; rN )j2 dr3 : : : drN :
V

(175)

Note that the total integral over both oordinates in n(r; r0) is equal to twi e the number of
unique ele tron pairs.
The ex hange- orrelation hole is des ribed by the fun tion g (r; r0), whi h is de ned
through
n(r; r0 ) = n(r)n(r0 )(1 + g (r; r0)):
(176)
If we put g = 0, the pair-distribution fun tion is equal to the produ t of the densities at the
two points r and r0 , whi h implies that the ele trons are un orrelated. However, g annot
be equal to zero for all r and r0 . The integral of n(r; r0) over r0 yields (N 1)n(r) while the
integral of n(r)n(r0 ) yields Nn(r). Hen e we arrive at the important sum rule
Z

g (r; r0) n(r0 ) dr0 = 1; all r:


111

(177)

In systems with a fra tional number of ele trons, the Kohn-Sham orbitals have fra tional
o upation numbers [657. Spe i ally, a ontinuous hange from the (N 1)-ele tron to the
N -ele tron system is obtained by a variation between 0 and 1 of the o upation number of the
highest o upied orbital in the N -ele tron system. One of the most important on lusions
from su h a formulation is that the energy "N;N of the highest o upied Kohn-Sham orbital
in the N -ele tron system (integer N ) is equal to the hemi al potential N [40, 658:

"N;N = N ;

(169)

where N = N , in nitesimal. That is, by the hemi al potential for integer N we here
mean, by de nition, the hemi al potential of a system with a fra tional o upation of the
N th Kohn-Sham orbital. The notation "N;M refers to the energy of the M th Kohn-Sham
orbital in the N -ele tron system.
. The band-gap dis ontinuity
Let us rst de ne the ionization energy I and the ele tron anity A for the N -ele tron
system:
I = EN 1 EN ; A = EN EN +1 ;
(170)
where EM denotes the ground-state energy of the M -ele tron system. In a ma ros opi
semi ondu tor with N ele trons in the fully o upied valen e bands, we an asso iate I
with minus the hemi al potential N of the N -ele tron system, and A with minus the
hemi al potential N +1 of the (N +1)-ele tron system (one (fra tional) ele tron in the lowest
ondu tion state). Hen e, from Eqs. (169) we obtain:

I = N = "N;N ; A = N +1 = "N +1;N +1 :

(171)

The quasiparti le band gap Egap is given by the di eren e between I and A:

Egap = I

A = "N +1;N +1

"N;N = x + "N;N +1

"N;N ;

(172)

where we have de ned x = "N +1;N +1 "N;N +1 , that is, the energy di eren e between
the highest o upied Kohn-Sham orbital in the (N +1)-ele tron system and the lowest uno upied Kohn-Sham orbital in the N -ele tron system. This di eren e is in general nite
[659, 660 and believed to be of the order of eV in semi ondu tors and insulators [6. The
last two terms in Eq. (172), "N;N +1 "N;N , give the band gap in the N -ele tron Kohn-Sham
system.
As the notation suggests, x is due to the ex hange- orrelation potential Vx in Eq. (168),
and is aused by a dis ontinuous jump in Vx on addition of an ele tron [659, 660, 661:
x = Vx ;N +1 (r) Vx ;N (r);

(173)

where the expli it r dependen e indi ates that the di eren e between the ex hange- orrelation
potentials in the (N +1)-ele tron system and the N -ele tron system is a position-independent
110

Formally, the Kohn-Sham potential an be obtained from the fun tional F [n. The rst
step is to de ne another universal fun tional T0 [n:

T0 [n = min
h jT^j i;
!n

(160)

where is any N -ele tron wave fun tion that yields the density n. That is, T0 is the lowest
kineti energy any wave fun tion an give under the onstraint that it must yield the density
n. The total-energy fun tional of the Kohn-Sham system is

EKS [n = T0 [n +

VKS (r)n(r) dr:

(161)

When the minimization in Eq. (160) is extended to in lude mixed states and fra tional
o upation, T0 [n has a well-de ned fun tional derivative, and we obtain, in analogy with
Eq. (158)


T0 [n
EKS [n
=
+ V = N :
(162)


n n=n0
n n=n0 KS
Comparing Eqs. (162) and (158), we see that VKS must be de ned by

(F [n T0 [n)
(E [n T0 [n)
=
+ Vext :


VKS =


n
n
n=n0
n=n0
It is ustomary to split the universal fun tional F [n
1Z
EH [n =
2

T0 [n into a Hartree pie e

n(r)n(r0 )

jr

r0

(163)

0
j drdr

(164)

and a remainder Ex [n whi h is alled the `ex hange- orrelation energy:'

F [n T0 [n = EH [n + Ex [n:

(165)

The Kohn-Sham potential an then be expressed in terms of Ex [n as


(EH [n + Ex [n)
VKS =
+ Vext = VH + Vx + Vext ;


n
n=n0

(166)

where VH is the ground-state Hartree potential

VH (r) =

n0 (r0 ) 0
0 dr

jr

(167)

and Vx is the so- alled ex hange- orrelation potential


E [n
Vx (r) = x
n(r) n=n0
109

(168)

When a fra tional total number of ele trons is allowed, the Rground-state energy and
density is obtained by minimizing E [n under the onstraint that V n(r) dr = N :


E [n +  N



n(r) dr

= 0;

(157)

where  is a Lagrange multiplier. In terms of density fun tional derivatives, we an therefore


write

E [n
= N ;
(158)

n n(r)=n0 (r)
where n0 (r) is the ground-state density. It an further be shown that if N is a noninteger
N is the hemi al potential of the N -ele tron system [652. For integer N the hemi al
potential is in general unde ned and N as a fun tion of N is dis ontinuous.
A ording to the theory of Hohenberg and Kohn [32 there is a unique ground state
belonging to ea h external potential. This one-to-one mapping between the density and the
external potential means that the exa t ground-state wave fun tion is also a fun tional of the
density. A given density orresponds to a parti ular external potential, and that potential
gives, for nondegenerate ground states, a unique ground-state wave fun tion of the Hamiltonian in Eq. (154). Sin e the ground-state wave fun tion is a fun tional of the density so
are all expe tation values of this wave fun tion.
b. The Kohn-Sham system
Kohn and Sham [33 show how a pra ti al omputational method an be onstru ted from
the density fun tionals of Hohenberg and Kohn. The idea is to asso iate the physi al system
of N intera ting ele trons with a titious system of N nonintera ting ele trons. We all this
titious system the `Kohn-Sham system' and the nonintera ting ele trons the `Kohn-Sham
ele trons.' The onne tion between the two systems is that they are de ned to have exa tly
the same ground-state density and hemi al potential.
The external potentials in the two systems are not the same. On the ontrary, the
external potential in the Kohn-Sham system { the Kohn-Sham potential { must be pre isely
that single-parti le potential that yields a ground-state density for the Kohn-Sham system
that is equal to the ground-state density of the intera ting system.
For nondegenerate ground states, the wave fun tion of the Kohn-Sham ele trons is a
Slater determinant of the N lowest orbitals i of the Kohn-Sham equations:



1 2
r + VKS (n0; r) i (r) = "ii(r);
2

n0 (r) =

ji(r)j2;

(159)

where the notation VKS (n0 ; r) means that VKS is a lo al single-parti le potential that is an
impli it fun tional of the exa t ground-state density n0 . The Kohn-Sham equations must be
solved self- onsistently so that both equations in Eq. (159) are ful lled.
108

Appendix A: Density Fun tional Theory


This Appendix gives a short overview of density fun tional theory. The purpose is to remind
the reader of those on epts and ideas that are built upon in the main text of this review. We
shall neither attempt a omplete review of density fun tional theory, nor follow a histori al
sequen e of presentation. For further review see, for example, Refs. [651, 652, 653, 654, 655.
a. Universal density fun tionals
The goal of density fun tional theory as introdu ed by Hohenberg and Kohn [32 is to nd
the exa t ground-state density and total energy of a system of N intera ting ele trons in
an external potential Vext . The ele trons are assumed to intera t pairwise via the Coulomb
intera tion. The Hamiltonian H^ for this system is
N
N
N
X
X
1 2 X
1
H^ =
r
+
+
Vext (ri );
i
i=1 2
i<j jri rj j i=1

(154)

where ri is the oordinate for the ith ele tron. To simplify the notation, we denote the rst
term in Eq. (154), the kineti -energy operator, by T^, and the se ond term, the Coulombintera tion operator, by V^Coul . These two terms are the same in all N -ele tron systems
onsidered, only the external potential di ers between systems. This invarian e of the kineti
and Coulomb operators in the Hamiltonian is the basis for the idea of universal fun tionals.
Following the formulation by Levy [618, 619 and Lieb [620, we de ne the density fun tional
F [n = min h jT^ + V^Coul j i;
(155)
!n(r)
where the minimization is over all N -ele tron wave fun tions that yield the given ele tron
density n(r). That is, F [n is the lowest expe tation value, or energy, of the Hamiltonian
T^ + V^Coul that an be obtained by any N -ele tron wave fun tion given that the density is
equal to n. This fun tional is universal in the sense that it does not in lude any dependen e
on the external potential. The total energy fun tional E [n for a spe i system is obtained
by addition of the intera tion with the external potential:

E [n = F [n +

Vext (r)n(r) dr:

(156)

The above formulation is valid for an integer number of ele trons. However, the de nition of
the fun tionals an be extended to noninteger ele tron numbers by the in lusion of mixtures
between states with di erent total number of ele trons in the minimization in Eq. (155)
[40, 656. For example, fra tional ele tron numbers between N and N +1 are obtained from
mixtures of N - and (N +1)-ele tron wave fun tions.
107

A knowledgements

It is a pleasure to a knowledge helpful omments from M. Alouani, F. Aryasetiawan,


J. Chen, A. G. Eguiluz, A. Fleszar, R. W. Godby, A. Gorling, O. Gunnarsson, P. Kruger,
M. Rohl ng, L. J. Sham, E. L. Shirley, J. E. Sipe, and U. von Barth. We thank F. Aryasetiawan and O. Gunnarsson, A. Gorling, and M. Rohl ng, P. Kruger, and J. Pollmann for
allowing us to use unpublished data; A. Fleszar, A. Gorling, and L. Steinbe k for a riti al
reading of the manus ript; A. G. Eguiluz, B. Farid, and G. D. Mahan for sending us material prior to publi ation; and J. Chen for providing pseudopotentials. W. G. A. gratefully
a knowledges ontinued ollaboration with L. Steinbe k, M. M. Rieger, and R. W. Godby
on the real-spa e/imaginary-time GWA.

106

for example, a Hartree-Fo k or LDA al ulation. Despite the xed-node approximation,


di usion Monte Carlo al ulations usually generate highly a urate wave fun tions.
Di usion Monte Carlo an be used to obtain the lowest energy eigenstate of a given
symmetry. Mostly indire t band gaps in solids have been omputed [645, 646, 647, sin e
the di eren e in total rystal momentum between the ex ited state and the ground state
ensures their orthogonality. However, Williamson et al. [612 show that, although in prin iple
di usion Monte Carlo is not useful for al ulations of dire t gaps, in pra ti e su h al ulations
an be done within the xed-node approximation.
To obtain the dire t gap at , for example, the highest valen e-band orbital in the
ground-state wave fun tion is repla ed by a ondu tion-band orbital. Without the xed-node
approximation this initial wave fun tion would again generate the ground state. However,
within the xed-node approximation this does not happen, sin e the nodal stru ture is not
the same in the initial state and the ground state, due to the di eren e between the valen eand ondu tion-band orbitals. Williamson et al. obtain a 3.7 eV gap in sili on (see Table
39) by implementing this form of di usion Monte Carlo.
The fa t that Monte Carlo methods an generate highly a urate densities makes these
methods parti ularly helpful in analyzing detailed features of density fun tional theory. For
example, Hood et al. [648 use variational Monte Carlo to al ulate the exa t form of the
ex hange- orrelation hole in sili on, in luding the dependen e on oupling onstant. Other
examples are the work by Knorr and Godby [649 and Engel et al. [650 who analyze the
Kohn-Sham potential for model semi ondu tors with the help of exa t densities obtained
from di usion Monte Carlo simulations. Also, Kent et al. [613 use variational Monte Carlo
to al ulate both density matri es and the full band stru ture of sili on (see Table 39 for
their value of the gap).

105

present on erning the nite frequen y aspe ts of this problem. The al ulations of opti al
oe ients in Se tion 31 are obtained by using time-dependent density-fun tional theory
with a stati LDA kernel to des ribe the e e t of ex hange and orrelation on the lo al
elds. The need for a s issors-operator orre tion to obtain a reasonable absorption spe trum
demonstrates that this simple kernel is inadequate for the des ription of semi ondu tor gaps.
Vignale and Kohn [632 have developed a time-dependent formalism based on fun tionals
of both density and urrent. They show that in this formalism lo al approximations are more
promising. Further, the theory an be ast in a form where the ele tron gas is des ribed
by a ontinuum uid model where the vis osity and elasti ity oe ients an be obtained
from parameters of the homogeneous ele tron gas [639, 640. One of the su esses of this
method is a derivation of the damping of olle tive modes in an inhomogeneous ele tron gas.
Appli ations to quantum wells give dampings of the orre t order of magnitude although
these appli ations also reveal some fundamental di ulties [641.
36. MONTE CARLO CALCULATIONS
In quantum Monte Carlo approa hes, statisti al sampling methods are used to al ulate
matrix elements { variational Monte Carlo [642 { or to propagate the imaginary-time
S hrodinger equation by numeri ally simulated di usion { di usion [643 or Green fun tion Monte Carlo [644. In both these methods, a real-spa e many-ele tron wave fun tion
representation allows the generation of highly a urate wave fun tions, in luding strong orrelation e e ts. In variational Monte Carlo, a parametrized form of the wave fun tion is
hosen and the total energy is then minimized by numeri al integration of the matrix elements of the Hamiltonian. In di usion Monte Carlo, the mathemati al equivalen e between
the imaginary-time S hrodinger equation and a real-time di usion equation is used to propagate the S hrodinger equation by simulated numeri al di usion of a olle tion of titious
parti les (\walkers") whose density orresponds to the wave fun tion. Propagation of the
imaginary-time S hrodinger equation exponentially proje ts out the ground state from any
initial state that is not orthogonal to the ground state. In this way, an exa t numeri al wave
fun tion for the ground state an be obtained from a reasonably a urate initial guess. Often
a variational Monte Carlo al ulation generates an initial wave fun tion for a more a urate,
and more omputationally ostly, di usion Monte Carlo al ulation.
Appli ation of di usion Monte Carlo is straightforward only for bosons, while for fermions
the antisymmetry of the wave fun tion is di ult to handle. If the antisymmetry is not
stri tly enfor ed, the numeri al simulation will in general lead to a bosoni ground state
even for a fermioni initial wave fun tion. The ommon way to avoid this problem is to for e
the wave fun tion to keep the nodal stru ture of the initial wave fun tion. This ` xed-node'
approximation [355 ensures that the obtained wave fun tion is antisymmetri . However, the
exa t ground state annot be found this way, sin e it is in general impossible to predi t the
orre t nodal stru ture. The wave fun tion found is instead the wave fun tion with the lowest
energy of all states with the given node stru ture. In pra ti e, the nodal stru ture of the
initial wave fun tion is given by a Slater determinant of single-parti le orbitals obtained from,
104

with some ex ited-state orbitals o upied. This Slater determinant is identi ed with the
~ i remains unknown.
wave fun tion i in the partitioning above, while the se ond part
The formalism of Frits he an be used to derive an expression for the band gap in semi ondu tors, whi h for sili on and diamond yields dire t band gaps in good agreement with
experiment. However, the expression for the band gap depends expli itly on the ex hange orrelation energy density and the ex hange- orrelation potential. To obtain numeri al values, Frits he and Gu [611 model the shape of the equal-spin ex hange- orrelation hole (see
Appendix A, Se tion d), from whi h the energy density and potential an be obtained, and
negle t the opposite-spin orrelation hole. In Table 39, we have in luded the gap values
for sili on and diamond obtained by assuming either a Gaussian or Lorentzian shape of the
ex hange- orrelation hole.
35. TIME-DEPENDENT DENSITY FUNCTIONAL THEORY
For nite systems, a pra ti al method for obtaining ex ited-state energies is to nd the
poles in the frequen y-dependent linear-response fun tions [629. Within density-fun tional
theory this approa h requires an extension of Kohn-Sham theory to time-dependent external
potentials. Runge and Gross [630 have shown that su h a generalization an be obtained
under general ir umstan es. However, the obtained density fun tionals depend on the
initial state, and the time dependen e of the external potential must be su h that it an
be expanded in a Taylor series in time. For a review of time-dependent density fun tional
theory see, for example, Ref. [631.
As for the time-independent ase, the ex hange and orrelation e e ts in linear response
are ontained in an ex hange- orrelation kernel Kx (q; ! ), whi h is now frequen y dependent.
For numeri al appli ations some approximation must be hosen for Kx (q; ! ). A useful kernel
at low-frequen ies and for slowly varying densities is given by the adiabati lo al-density
approximation [570, in whi h the frequen y dependen e is negle ted and the stati LDA
kernel is used. However, Vignale and Kohn [632 show that lo al-density approximations fail
at nite frequen ies. In parti ular, for intera ting ele trons in a harmoni potential exa t
onstraints [633, 634 on the form of Kx (q; ! ) are obtained, whi h onstraints an only be
satis ed by non-lo al kernels. A entral issue in time-dependent density fun tional theory is
therefore to nd improved approximations to Kx (q; ! ).
Many of the theories des ribed in Se tions 33 and 34 above an be generalized to in lude
time dependen e, ea h of them orresponding to a parti ular approximation to Kx (q; ! ).
Examples are the nonadiabati lo al-density kernel of Gross and Kohn [635, whi h violates
the harmoni -potential onstraints, and exa t-ex hange kernels [636, 637. The oupling onstant perturbation theory of Gorling an also be extended to time-dependent potentials,
from whi h theory formally exa t orrelation an be systemati ally in luded in Kx (q; ! )
[638.
For semi ondu tors, as we saw in Se tion 32 on erning density-polarization fun tional
theory, the divergen e of Kx (q; ! ) as q!0 plays a entral role in opti al response. This
aspe t of Kx (q; ! ) has yet to be fully understood in the stati limit, and nothing is known at
103

ex ited-state on guration 2s2 yields an extremum of E [n while the on guration 1s2s does
not yield an extremum. That is, they nd E [n2s2 = E2s2 and E [n1s2s < E1s2s . There is no
me hanism in general to identify whi h ex ited state an be obtained from the ground-state
fun tional, so no pra ti al approa h is obtained from these onsiderations.
Theophilou and ollaborators [622, 623 demonstrate that ex ited-state energies an be
obtained from an extension of density fun tional theory to the sum of the lowest-lying states.
For the ground state, the Rayleigh-Ritz variational prin iple states that the ground-state
wave fun tion is the one that minimizes the expe tation value of the Hamiltonian. An
extension of this prin iple says that the sum of the N lowest energies is obtained as the
minimum of the sum of the expe tation values of the Hamiltonian H^ with respe t to N
orthogonal states:
N
N
X
X
min
h
i jT^ + V^Coul j i i = Ei :
(153)
h j i= i
i
Based on this extended variational prin iple a density fun tional theory an be onstru ted
in omplete analogy with the standard Hohenberg-Kohn formulation. The density obtained
from this theory is the sum of the densities of the N lowest eigenstates, and the energy is
the sum of the orresponding energies.
The ex ited-state energy of a given state an be found with this extended formulation if
the energies of all the lower-lying states are known. For example, to obtain the energy of
the rst ex ited state, the ground-state energy is rst al ulated and then the sum of the
ground-state and the ex ited-state energies. From these two al ulations, the ex ited-state
energy is obtained by subtra tion. This so- alled ensemble density-fun tional theory an
be generalized to arbitrary mixtures of states, that is, sums of states with unequal weights
[624, 625. However, the fun tional itself is di erent for every mixture, and it is not lear how
to obtain these fun tionals in pra ti e. This method has been used for atoms and mole ules
[599 but, as far as we know, not in semi ondu tors.
Valone and Capitani [626 use a variational formulation for the operator (H^ U )2 , where
U is a free parameter, to onstru t a fun tional R2 [n; U; Vext that when minimized yields
the exa t ex ited-state energy losest to U . A s an of U over a range of energies an then
in prin iple yield all ex ited states in that range. However, as indi ated in the fun tional
dependen e of R2 , this fun tional is impli itly and nontrivially dependent on the external potential and is not universal as is the Hohenberg-Kohn fun tional. The potential dependen e
makes this theory impra ti al for appli ation to real systems.
Frits he [627, 628 formulates a generalized Kohn-Sham theory for ex ited states based
~ i , where i is a Slater
on a formal partitioning of any ex ited state i into a sum i = i +
~ i gives no
determinant that yields the exa t ex ited-state density ni , while the remainder
ontribution to ni . By adiabati swit hing of the oupling onstant, a mapping between an
ex ited state in a nonintera ting Kohn-Sham system and an ex ited state in the intera ting
system an be obtained. During the swit hing of the oupling onstant the density is kept
xed to the exa t ex ited-state density of a given ex ited state in the intera ting system. The
Kohn-Sham potential in this formalism is therefore di erent for ea h ex ited state, and the
non-intera ting system is in general in an ex ited state des ribed by a Slater determinant
i

i;j

102

In the method of Gorling [617, the adiabati onne tion is assumed to exist not just
between the ground states of the Kohn-Sham and the intera ting system, but also between
all the ex ited states of the two systems. Perturbation theory to in nite order in the oupling
onstant then gives all the ex ited-state properties of the intera ting system as fun tions of
the omplete set of Kohn-Sham orbitals and energies, in luding the orbitals uno upied in
the ground state. These orbitals and energies are all determined by the Kohn-Sham potential
and are in that sense fun tionals of the exa t ground-state density, sin e the Kohn-Sham
potential is uniquely determined by the ground-state density.
In the Kohn-Sham system, the ex ited states are given by all possible Slater determinants that an be formed from the omplete set of single-parti le Kohn-Sham orbitals. By
onstru tion, the ground-state determinant yields the orre t ground-state density, while the
ex ited Kohn-Sham determinants yield densities and energies that are not equal to the exa t
ex ited-state energies and densities. However, by the assumed adiabati onne tion between
the Kohn-Sham and the intera ting system, the exa t energies and densities are obtained as
an in nite perturbation series in the oupling onstant. For example, in the oupling onstant expansion of the band gap the zeroth-order term is the Kohn-Sham gap, the rst-order
orre tion is the ex hange ontribution, and the higher-order terms are orre tions due to
orrelation. No al ulations for semi ondu tors using this method have been published to
date, and the onvergen e properties of the perturbation expansion are not known.
34. FUNCTIONALS BASED ON EXCITED-STATE DENSITIES
In Appendix A, the universal fun tional F [n that appears in the Hohenberg-Kohn theory
as re ned by Levy [618, 619 and Lieb [620 is de ned by a onstrained minimization of
the kineti and Coulomb energies over all N -parti le wave fun tions that yield the given
density n:
F [n = min
h jT^ + V^Coul j i:
(152)
!n
That is, that fun tional is de ned for a very large set of densities, and in parti ular for any
well-behaved ex ited-state density. The total energy E [n is obtained
by adding the energy
R
of the intera tion with the external potential: E [n = F [n + Vext(r)n(r) dr.
What is the relationship between the exa t energy Ei of the ith ex ited state and the
energy E [ni obtained from the exa t density of the ith ex ited state? From the minimization
in the onstrained sear h in Eq. (152), it follows that the fun tional value of E [ni must be
lower or equal to the exa t ex ited state energy: E [ni  Ei . E [ni is by onstru tion
the lowest energy any wave fun tion an have for the given density ni , however, the wave
fun tion that minimizes E [ni does not have to be equal to the ex ited state wave fun tion,
even though they both yield the same density.
Perdew and Levy [621 show that the equal sign in the relation E [ni  Ei holds if and
only if the density ni yields an extremum for E [ni . However, all ex ited states do not yield
an extremum for E [ni . Perdew and Levy take as an example two nonintera ting ele trons in
an attra tive Coulomb potential, and show that, with the ground-state on guration 1s2 , the
101

Slater determinants  that yield the given density n.

T0 [n = min
hjT^ji:
!n

(149)

To in lude ex hange, Seidl et al. de ne a new fun tional G0 that besides T^ also in ludes
the Coulomb intera tion V^Coul , but with the minimum still taken over Slater determinants
 with N orbitals i :
n

hjT^ji + EH [fig + Ex[fi g ;


G0 [n = min
hjT^ + V^Coul ji = min
!n
!n

(150)

where EH is the Hartree energy and Ex is the ex hange energy

Ex [fi g =

i (r)j (r0 )j (r)i (r0 )

jr

i<j

r0

drdr0:

(151)

Whereas in the standard formulation, as shown in Appendix A, the ex hange- orrelation


energy is de ned by Ex [n = F [n EH [n T0 [n, where F [n is the Hohenberg-Kohn
fun tional, Seidl et al. de ne a new fun tional G [n = F [n G0 [n. By onstru tion, G
is expe ted to be dominated by orrelation, even though some ex hange and kineti energy
remain in G .
The `exa t'-ex hange generalized Kohn-Sham equations are similar to the Hartree-Fo k
equations, but not identi al to them due to the formally exa t treatment of orrelations.
However, if G is negle ted the Hartree-Fo k equations are obtained. Note, therefore, that
with this generalization the Kohn-Sham equations are non-lo al. We also know that in this
ase the Kohn-Sham band gap will typi ally be 5{10 eV larger than experiment, sin e this is
the result obtained in Hartree-Fo k al ulations. However, by using s reened ex hange Seidl
et al. nd better agreement with experiment, even though the gaps in Ge and GaAs are now
half an eV too small. In s reened ex hange, an extra fa tor exp( kT F jr r0 j) is introdu ed
in the ex hange integral in Eq. (151), where kT F is the Thomas-Fermi s reening onstant for
the average density. In Table 39, we have in luded the sX-LDA gaps of Seidl et al., whi h
are al ulated with the s reened-ex hange fun tional and a lo al-density approximation for
G .
Coupling- onstant perturbation theory. The ex ited-state theory of Gorling [617 gives all
ex ited-state properties as fun tionals of the exa t ground-state density of the N -ele tron
system. In the standard formulation of Kohn-Sham theory, a formal onne tion between
the ground-state in the nonintera ting Kohn-Sham system and the exa t ground state is
obtained if the Coulomb oupling onstant e2 is adiabati ally swit hed o . See Appendix
A, Se tion e, for further details. During the swit hing, the density is kept xed by the
help of a oupling- onstant-dependent potential hosen so that the density is independent
of the oupling onstant and equal to the exa t ground-state density. In the limit of no
oupling this external potential is by onstru tion equal to the Kohn-Sham potential for the
nonintera ting system.
100

Sin e the dis ontinuity x is is believed to be of the order eV in semi ondu tors, pra ti al
appli ations of the SCF method require a density fun tional that aptures the dis ontinuity.
Lo al-density approximations, in luding gradient orre tions, an therefore not be used to
al ulate the band gap in semi ondu tors. When a single ele tron is added to a ma ros opi
system, the density does not hange; therefore lo al-density approximations give "N +1;N +1 =
"N;N +1 . In pra ti e, only non-lo al, orbital-dependent fun tionals give rise to a potential
dis ontinuity.
Exa t ex hange. Fun tionals based on an exa t treatment of ex hange yield Kohn-Sham
potentials that in lude the ex hange part x of x = x + . Krieger, Li, and Iafrate (KLI)
[601 show how the Kohn-Sham potential for exa t ex hange an be al ulated in pra ti e in
nite systems. Earlier, Sharp and Horton [602 and Talman and Shadwi k [603 showed in
prin iple how the exa t-ex hange potential, the so- alled optimized e e tive potential (OEP),
an be derived, but KLI demonstrate approximations that lead to omputationally simpler
equations with little loss of a ura y. Exa t ex hange methods (EXX) for extended systems
have been developed by Bylander and Kleinman [604, 605, 606, who use the simpli ed KLI
version, by Kotani and Akai [607, and by Gorling [608. Stadele et al. [609 apply the
formally exa t formulation of Gorling to several semi ondu tors.
Table 39 olle ts the exa t-ex hange values for the dire t band gaps of Si, Ge, diamond,
and GaAs. For ompleteness, we also in lude the orresponding experimental, LDA, GWA,
and Hartree-Fo k gaps, and gaps obtained from other methods dis ussed below. The values
related to exa t ex hange methods are in rows 5{7: EXX-KS are the Kohn-Sham gaps
"N;N +1 "N;N ; EXX-x are the SCF gaps "N;N +1 "N;N + x ; and KLI-KS are the KohnSham gaps obtained with the approximation suggested by Krieger, Li and Iafrate. The
Kohn-Sham gaps of Stadele et al. for Si and C agree well with experiment, while the KLI
values of Bylander and Kleinman and the EXX values of Kotani and Akai, who used a nonrelativisti KKR band stru ture within the atomi -sphere approximation, deviate by up to
0.7 eV from experiment. The SCF gaps, whi h in lude the band-gap dis ontinuity of the
ex hange potential, are lose to the Hartree-Fo k values and overestimate the experimental
gaps by 5{8 eV. The good agreement between experiment and the EXX Kohn-Sham gaps
together with the large values of x (5{10 eV) implies that  is equally large but negative.
Generalized Kohn-Sham s hemes. A di erent solution to the band-gap problem has been
proposed by Seidl et al. [610. The Kohn-Sham equations are generalized so that more of
the gap is given by the Kohn-Sham gap and less by the dis ontinuity. Formally, this redistribution is a hieved by modifying the original partition of the total-energy fun tional into
kineti , Hartree, external, and ex hange- orrelation fun tionals. Part of the the ex hange orrelation energy is added to the kineti energy before the fun tional is de ned through the
onstrained sear h approa h. In su h a formulation, the Kohn-Sham potential is non-lo al.
One generalized Kohn-Sham theory dis ussed by Seidl et al. is based on exa t in lusion
of ex hange. In the original Kohn-Sham formulation, for nondegenerate ground states, the
kineti -energy fun tional is de ned by minimizing the kineti energy operator T^ over all

99

VII. Ex ited states within density fun tional theory


Within density-fun tional theory, there are several methods to dire tly al ulate ex ited
states. Some of these methods yield band gaps in semi ondu tors without need for quasiparti le theory. This se tion gives a short des ription of these alternatives to GWA al ulations.
To stru ture the presentation, we lassify the methods a ording to the density on whi h
the density fun tionals are based. For time-independent fun tionals either the ground-state
density or the ex ited-state density an be used to onstru t a density-fun tional theory for
ex ited states. These two ases are dis ussed in Se tions 33 and 34, respe tively. Timedependent density fun tional theory, outlined in Se tion 35, an also be used to nd ex itedstate properties by analysis of various response fun tions. Finally, Monte Carlo methods, as
dis ussed in Se tion 36, an yield ex ited states and generate highly a urate densities for
the purpose of detailed analysis of density fun tional theories.
Most of the work with these new methods has been done for atoms and small mole ules
rather than for extended systems. For a review of results for atoms and mole ules, see
the re ent arti le by Nagy [599. Here, we give a brief des ription of the ideas behind the
methods, and fo us the dis ussion on the band gaps in semi ondu tors, even though that
aspe t represents only a small fra tion of the published work.
The material in this hapter deals with extensions to ex ited states of onventional
density-fun tional theory, whi h is onstru ted to give only the ground-state density and
energy. In the main text, we assume that the reader is familiar with standard HohenbergKohn and Kohn-Sham theory. However, for the reader who needs a reminder, we give a
short overview in Appendix A of those density-fun tional on epts that are entral to the
dis ussion below.
33. FUNCTIONALS BASED ON GROUND-STATE DENSITIES
The SCF method. With a slight extension of the original Hohenberg-Kohn formulation
the theory is valid not only for ground states but for any state that is the lowest of its
symmetry lass [600. The ex itation energies between two su h states of di erent symmetry
an therefore be al ulated as an energy di eren e between two separate al ulations. This
approa h is alled the SCF method [37, sin e a di eren e between two self- onsistent
energy al ulations is taken.
The band gap in a semi ondu tor, with N ele trons in the fully o upied valen e orbitals,
is equal to the di eren e between the energies of the highest o upied Kohn-Sham orbital
in the (N +1)-ele tron ground state and the highest o upied Kohn-Sham orbital in the N ele tron ground state: Egap = "N +1;N +1 "N;N , where the notation "N;M refers to the M th
Kohn-Sham orbital in the N -ele tron system. The di eren e between the energies "N +1;N +1
and "N;N +1 (lowest uno upied orbital in the N -ele tron system) is, by de nition, equal to
the dis ontinuity x of the Kohn-Sham potential on addition of an extra ele tron to the
N -ele tron system: Egap = "N;N +1 "N;N + x (see Appendix A, Se tion ).

98

potential approximately proportional to the gap mismat h is also dis ussed by Godby and
Sham [598 in an analysis of band bending at doped S hottky (metal-semi ondu tor) interfa es.
Aulbur et al. [592 onsider the onsequen es of Eq. (148) and its extension to nonlinear
response for most semi ondu tors and insulators for whi h data exists. They show that
is remarkably material independent and of order 0.25 in most small- and medium-gap
materials, as shown in Fig. 50. For large-band-gap materials the value for goes down to
about 0.1. These numbers were obtained by using the experimental values for  and the
LDA sus eptibility for KS . The latter approximation is motivated by the observation that
LDA, being derived from a metalli system, ompletely ignores any e e t of Ex but des ribes
ground state properties well. Hen e, it is reasonable to assume as a rst approximation that
LDA is lose to KS .
In summary, the Kohn-Sham ele trons in density fun tional theory are titious parti les
whi h besides the physi al potential are a ted upon by a titious ex hange- orrelation potential. Formally, this extra potential derives from the divergen e of the ex hange- orrelation
kernel in exa t Kohn-Sham theory for in nite insulators. This divergen e is absent in LDA.
All al ulations to date of opti al response in semi ondu tors and insulators have negle ted
the existen e of a ma ros opi ex hange- orrelation potential. When this extra potential
is onsidered in opti al response al ulations, agreement with experiment an be obtained
without adjustments to the energy spe trum.

97

felt by the Kohn-Sham ele trons besides the physi al eld. In general, for longitudinal,
s alar potentials we an de ne E = rV = iqV and n = r  P = iq  P. Then an
indu ed ex hange- orrelation potential Vx = Kx n / n=q 2 is equivalent to an ex hange orrelation ele tri eld dire tly proportional to the indu ed polarization, Ex / P. The
latter formulation has given this version of Kohn-Sham theory for in nite insulators the
name `density-polarization fun tional theory.'
The problem with the band gap mismat h between the quasiparti le and the Kohn-Sham
spe trum has now been put in a di erent light than in our dis ussion in the previous se tions, where the fo us was on how to adjust the gap. Con erning opti al response at long
wavelengths, the Kohn-Sham pi ture is very di erent from the quasiparti le pi ture. The
quasiparti les are driven by the physi al ele tri al eld and need a orre t band stru ture to
give results lose to experiments. On the other hand, the titious Kohn-Sham ele trons inherently will not have the orre t band-stru ture and must therefore be driven by a titious
additional ele tri eld whi h exa tly ompensates for the spe tral di eren es and ensures
that the orre t density, or polarization, is indu ed as guaranteed by density fun tional theory in the stati limit.
b. Real materials
The above dis ussion demonstrates only a qualitative way in whi h density-fun tional theory
an give orre t response, but there is no re ipe yet that yields a numeri al expression for
the ex hange- orrelation eld. However, as dis ussed by Aulbur et al. [592, the fa t that
this eld is proportional to the indu ed polarization allows us to gain some important insight
about its strength and qualitative behavior.
Let us de ne the parameter to be the assumed onstant of proportionality between
the ex hange- orrelation ele tri eld and the polarization, Ex = P. From the de nition
of the sus eptibility , P = EH , where EH is the physi al (Hartree + external) eld, we
obtain Ex = EH . Further, in the Kohn-Sham pi ture we have P = KS (EH + Ex ). That
is, the Kohn-Sham ele trons are driven by the physi al eld plus the ex hange- orrelation
eld and the indu ed polarization is given by their response fun tion KS , whi h is the
independent-parti le sus eptibility given by the Kohn-Sham band stru ture. By onstru tion, the polarization must be the same in both pi tures. This yields
P

= EH = KS (EH + EH ):

(147)

Hen e, by elimination of EH from the se ond equality:

= 1=KS

1=:

(148)

Due to the too small gap in the Kohn-Sham spe trum, we expe t KS > and therefore
that is negative. Further from the assumption that the main di eren e between the quasiparti le spe trum and the Kohn-Sham spe trum resides in the energy di eren es, not the
wave fun tions, we obtain from Eq. (132) ' =(Egap ). An indu ed ex hange- orrelation
96

onstant eld, with areful onsideration of surfa e e e ts, or the long-wavelength limit an
be taken in the in nite-sample results. Here we adopt the latter approa h and fo us on
the long-wavelength limit of opti al response in the type of bulk formulations we use in the
previous se tions.
In Appendix A, we de ne the ex hange- orrelation potential Vx (r) = Ex [n=n(r),
whi h is the additional potential besides the physi al potential felt by the Kohn-Sham ele trons. By `physi al potential' we mean the ele tri al potential that would a t on a weak test
harge inside the sample. The physi al potential onsists of the external potential and the
Hartree potential. The titious Kohn-Sham ele trons are in addition a ted upon by the
ex hange- orrelation potential, whi h by onstru tion is ne essary to yield the same density
in the Kohn-Sham system as for the ele trons in the real, intera ting system.
In linear response, the ex hange- orrelation potential an be expanded to rst order in
the density hange. The ex hange- orrelation kernel Kx , whi h is the response fun tion
giving the indu ed ex hange- orrelation potential in terms of the indu ed density, is given
by the se ond fun tional derivative of the ex hange- orrelation energy:

Z
2 Ex [n
0
0
0
0
Vx (r) = Kx (r; r )n(r ) dr ; Kx (r; r ) =
;
(144)

n(r)n(r0 ) n=n0
where n0 is the ground-state density. For the Kohn-Sham ele trons this indu ed potential
must be added to the indu ed Hartree potential. The total indu ed potential a ting on the
Kohn-Sham ele trons therefore is

Vind (r) =

jr

+ Kx (r; r0) n(r0 ) dr0 :


r0 j

(145)

When lo al- eld e e ts are disregarded, we an write in momentum spa e:


!

4
Vind (q) = 2 + Kx (q) n(q):
q

(146)

The key point of the work by Gonze, Ghosez, and Godby is that in an insulator the
ex hange- orrelation kernel should be expe ted to have a 1=q 2 divergen e just like the
Coulomb potential in the Hartree term. This assertion has been shown to be true in model
al ulations [595. In a di erent language, the 1=q 2 divergen e of Kx means that the KohnSham ele trons feel a ma ros opi potential di erent from the physi al ele tri al potential.
In LDA, Kx goes to a onstant as q ! 0 and is unimportant ompared to the 1=q 2
divergen e of the Coulomb potential. This niteness of Kx in LDA is due to the metalli
hara ter of a homogeneous ele tron gas whi h is used to ompute the LDA kernel. Hen e,
despite the su ess of LDA for many material properties, LDA ompletely fails to des ribe
the divergen e in Kx expe ted in insulators.
The dis usion above on erning potentials and density an be re ast in terms of ele tri
elds and polarization. Instead of the long-wavelength omponent of the density, we an
onsider the indu ed polarization P and a orresponding ex hange- orrelation ele tri eld
95

opti al rotatory power is the ability of rystals with a hiral stru ture to rotate the plane of
polarization of light passing through. Table 38 shows the e e t of lo al elds on the diele tri
onstant, the se ond-order sus eptibility and the rotatory power of selenium and -quartz.
For " in both materials and for (2) in quartz, the orre tions are modest redu tions. For
(2) in Se there is a 33% positive orre tion. Finally, in the rotatory power the lo al elds
dominate the response { in -quartz the lo al- eld orre tion in reases the rotatory power
by a fa tor of eight, while in Se the lo al elds hange the sign and more than double the
absolute value.
The al ulations for the rotatory power annot be made with the s alar theory of opti al
response des ribed above, sin e the physi al e e t is a rotation of polarization and requires
a ve tor des ription. Therefore a generalization to ve tor response in terms of indu ed urrents and ve tor potentials has to be made [543, 583, 587. However, one an for wavelengths
mu h longer than the latti e onstant use a hybrid s heme that treats the slowly varying
elds by ve tor theory but uses s alar theory for the lo al elds [583, 588, 589, 590, thereby
greatly simplifying the treatment and avoiding the use of time-dependent urrent-density
fun tional theory.
32. DENSITY-POLARIZATION FUNCTIONAL THEORY
In the stati limit, the indu ed response to a weak perturbing potential an be obtained
from a ground-state al ulation and should therefore be obtained exa tly by Kohn-Sham
perturbation theory. This fa t has always been the strong, and just, argument made by
opponents to the s issors-operator approa h, whi h arti ially adds a non-lo al potential to
a theory that should be able to give the orre t low-frequen y opti al reponse by using an
appropriate Kohn-Sham potential. However, there is no doubt that LDA does not su e due
to the band-gap problem, and there are indi ations that even in exa t Kohn-Sham theory a
large gap mismat h exists, see Appendix A, Se tion .
a. Divergen e of Kx
A solution to this apparent paradox has re ently been presented by Gonze, Ghosez, and
Godby [537. They point out that in an in nite sample the ex hange- orrelation potential in
Kohn-Sham theory an be divergent in the long-wavelength limit. In a system with a gap,
within whi h a nite ele tri eld an exist and a nite polarization an be indu ed, great
are has to be applied when the limit of in nite sample size is taken within density fun tional
theory. The dis overy of Gonze, Ghosez, and Godby has important onsequen es for many
situations where bulk polarization o urs [591, 592, 593, 594, 595, 596, 597, not least for
ferroele tri s, but here we dis uss only the ne essary revision of linear response theory.
Let us rst state unequivo ally that there are no aws in the original work by Hohenberg
and Kohn [32, and Kohn and Sham [33. Their work addresses nite systems. The only
question is how the limit of in nite extent should be taken. This limit an be approa hed in
two ways: either the in nite-volume limit an be taken for the nite-size theory in a weak
94

out only re ently by Chen et al. [573. Earlier work had invariably assumed that only the
linear lo al- elds are important in non-linear response. However, Chen et al. show that the
non-linear lo al elds are of equal importan e. For example, for se ond-harmoni generation
we must onsider lo al elds both at the driving frequen y ! and at the se ond harmoni 2! .
It an also be shown analyti ally that for s alar potentials the dominant term of the linear
lo al eld is exa tly twi e of the dominant term of the nonlinear lo al eld, leading to a 50%
in rease in the lo al- eld orre tion ompared to previously published results. The typi al
orre tion due to lo al elds is therefore about 15% for se ond-harmoni generation, but
with large variation in strength and an o asional hange of sign.
Besides the work of Chen et al. [573, several other authors dis uss nonlinear response
in semi ondu tors, although Chen et al. are the only ones that onsider the full e e t of
lo al- eld orre tions. The plane-wave pseudopotential method, used by Chen et al., was
developed by Levine and Allan [536, 541, 567, 568 who show how to in lude a s issors shift
in the velo ity gauge. Their method is mostly applied in the long-wavelength limit [540, 542,
although frequen y dependen e below the gap an be obtained [575.
Sipe and oworkers [538, 566 make a detailed omparison between the velo ity-gauge and
length-gauge approa hes and nd that a simpler formulation than the Levine{Allan approa h
an be obtained when working in the length gauge. The length-gauge formulation is used
by Hughes and Sipe for GaAs and GaP [556 and by Hughes, Wang and Sipe for GaN and
AlN [577. They al ulate both the real and imaginary part of (2) for frequen ies up to well
above the absorption threshold within a s issors-shift approa h using an LDA FLAPW (fullpotential linearized augmented plane-wave) band stru ture, but no lo al- eld orre tions are
in luded. The formulation of Aversa and Sipe is also implemented by Rashkeev et al. [576
using an LMTO (linearized mun-tin orbitals) band-stru ture. They too study the frequen y
dependent (2) and added BN and SiC to the materials studied by Hughes et al. The arti le
by Rashkeev et al. also in ludes a detailed dis ussion of the strengths and weaknesses of
the s issors-shift approa h. Adolph and Be hstedt [578 al ulated the frequen y dependent
(2) for GaP, GaAs, InP, InAs and SiC with a plane-wave-pseudopotential method at the
theoreti al latti e onstants. They use s issors shifts for the III-V ompounds but dis uss a
more sophisti ated momentum- and band-dependent self-energy shift in SiC.
The opti al response al ulations des ribed so far have been done by sum-over-states
methods, but an alternative exists. Dal Corso et al. [552 use the so alled `2n + 1' theorem
[579 to derive a di erent and more e ient numeri al method for se ond-order response
within time-dependent density fun tional theory. The 2n+1 theorem in this ontext expresses se ond-order response fun tions (derivable from third-order derivatives of the total
energy) in terms of rst-order hanges in the wave fun tion. The al ulations by Dal Corso
et al. are performed at theoreti al latti e onstants far from the experimental ones, whi h
strongly a e ts their values. However, their method should lead to the same results as others
at the experimental latti e onstants.
The relatively modest lo al- eld orre tions we have seen up to this point are not a
general rule. Jonsson et al. [583 al ulate the lo al- eld orre tions to the opti al rotatory
power of -quartz and selenium and nd that the lo al elds dominate the response. The
93

P
where Hk = HkLDA +  j kih kj. Eq. (143) must be true for all v , , and k, so in the
velo ity gauge the velo ity matrix elements in the s issors-shift approa h are given by the
LDA velo ity matrix elements s aled by ("vk " k + )=("vk " k).

b. Numeri al results
The numeri al results below for lo al- eld e e ts in semi ondu tors and insulators are all
based on an extension to the Adler{Wiser expression in Eq. (139), whi h extension treats the
lo al elds in the time-dependent lo al-density approximation [570, rater than in RPA (timedependent Hartree approximation). In this extension, ex hange and orrelation e e ts in the
indu ed ele tron density are al ulated self- onsistently within LDA. For further details, see
the referen es ited in the following dis ussion.
Columns two and three in Table 35 show typi al lo al- eld orre tions to the diele tri
onstant. Invariably a redu tion of " by 5{10% is obtained. These results are onsistent
with the the e e t of lo al- eld orre tions on the absorption spe trum shown in Fig. 39.
The weight in the dominant peaks in "2 (! ) shifts somewhat to higher frequen ies, ausing a
redu tion in ".
In se ond-order response, the lo al elds give a larger orre tion { generally redu ing
(2) , but o asionally in reasing it. Table 37 shows the e e t of both the s issors orre tion
and the lo al elds on (2) for those of the previously dis ussed materials that la k inversion
symmetry, whi h is a prerequisite for a non-zero se ond-order response. The LDA values are
too large by as mu h as a fa tor of two, with the severest errors for the smaller gap materials.
The lo al- eld orre tions are of the order of 10-20%, and are negative ex ept for the zzz
omponent in SiC, whi h shows a 13% in rease. Despite the limited experimental data, we
an see a trend similar to that found for " { the s issors-operator approa h works well for the
smaller-gap materials, but an over orre tion is obtained for the larger-gap materials, here
exempli ed by SiC and GaN.
Hughes and Sipe [556 make an important observation: It is not lear that the experimental values for (2) are a tually orre t. Hughes and Sipe nd that their theoreti al values for
the se ond-harmoni oe ient with a s issors- orre ted band stru ture were quite far from
experimental values in, for example, GaAs and GaP. However, they found lose agreement
with re ent measurements of the linear ele tro-opti oe ient given by (2) (! ; !; 0) in ontrast to the se ond-harmoni oe ient (2) (2! ; !; ! ). The se ond-harmoni (SH) oe ient
gives the polarization at 2! indu ed by a eld at ! , while the ele tro-opti (EO) oe ient
gives the polarization at ! from a eld at ! and a stati eld. Formally, these two oe ients
should be equal in the stati limit, while the experimental values disagree by almost a fa tor
(2)
of two. For example, in GaAs (2)
SH;expt = 162  10 pm/V [571 and EO;expt = 99:8 pm/V
[556, 574, while some of the theoreti al values are 172 pm/V (pseudopotential) [575, 96.5
pm/V (FLAPW { full-potential linearized augmented plane-wave) [556, and 104.8 (LMTO
{ linearized mun-tin orbitals) [576. All these al ulations were done with s issors-shifted
LDA band stru tures. Clearly, both more experimental and theoreti al work is alled for.
The theory for lo al- eld orre tions to non-linear response has been orre tly worked
92

In numeri al implementations, two alternative forms of the Adler-Wiser formalism have


been used: (i) the length-gauge formulation of Sipe and oworkers [538, 566 based on matrix
elements of the position operator, whi h was used in Eq. (132); and (ii) the velo ity-gauge
formulation developed by Levine and Allan [535, 536, 541, 567, 568. These two formulations
di er by the way the matrix elements of type h kj exp(iq  r)jv k0 i are evaluated.
The length-gauge formulation an be obtained by an expansion in q of the exponential
exp(iq  r):
h kj exp(iq  r)jvk0i ' iq  h kjrjvkik;k :
(140)
The q-independent term in the expansion, h kjv k0 i, is zero due to the orthogonality of
orbitals from di erent bands. When Eq. (140) is used in the Adler-Wiser formula we obtain
the expression for  given in Eq. (132), if we identify the x-dire tion with the dire tion along
q, and if we anti ipate that the intraband matrix elements do not ontribute when all the
band-indi es and k ve tors are summed over.
The dire t expansion in Eq. (140) is valid only for interband matrix elements, sin e the
position operator is not well de ned for intraband matrix elements. A detailed derivation of
Eq. (132) requires a more areful treatment of intraband matrix elements [538, 566. Further,
when the Hamiltonian has non-lo al omponents, due to pseudopotential terms or self-energy
orre tions, additional ompli ations arise. These points have been dis ussed extensively in
re ent literature [538, 561, 569.
In the velo ity-gauge formulation, the exponential is not expanded in terms of q. Instead
the matrix element h kj exp(iq  r)jv k0 i, whi h is taken between the full Blo h states integrated over all spa e, is reformulated in terms of the periodi part of the Blo h states and
the integration limited to the volume
of a unit ell in the rystal:
1
1
h
kj exp(iq  r)jv k0i = h kjv k + qik+q;k :
(141)
V

Now the expansion in q an be performed by k  p perturbation theory, whi h yields


0

h kjvk + qi = h kj

jnkihnkjq  rk Hkjvki = h kjq  rkHkjvki :


("vk

"nk )

("vk

" k )

(142)

Instead of a position operator, the velo ity operator vk  i[Hk ; r = rk Hk appears, and
ea h matrix element also yields an extra energy denominator. Hen e, in the velo ity gauge
the formula for  will ontain two velo ity matrix elements and three energy denominators.
When the s issors-operator approa h is used, it is ru ial to re ognize the di erent origins
of the three energy denominators in the velo ity gauge. Only one energy denominator should
be shifted by ; the other two should remain unshifted, and the velo ity matrix element
should be taken with respe t to the LDA Hamiltonian without the shift. Sin e the wave
fun tions are un hanged, the overlap h kjv k + qi must be the same in LDA and in the
s issors-operator approa h, whi h requires:
h kjrkHkjvki = h kjrkHkLDAjvki ;
(143)
"vk " k + 
"vk " k
91

to in lude quasi-parti le and other many-ele tron e e ts.


31. LOCAL-FIELD EFFECTS IN OPTICAL RESPONSE
In semi ondu tors and insulators, the inhomogeneity of the density distribution leads to
internal ele tri elds that vary over distan es omparable to the latti e onstant. As shown
below, su h lo al elds give rise to about 10% orre tions in ", 10{30% orre tions in (2) ,
and an lead to dominant orre tions in properties su h as the opti al rotatory power.
a. De nitions and gauge
In the notation of Chapter II, an external potential Vext(q; ! ) of wave ve tor q and frequen y
! yields a total internal ele tri al potential Vtot given by
Vtot;G (q; ! ) = " 1 Vext (q; ! ):
(136)
G0

1 appears on the
Note that only the G0 = 0 omponent of the inverse diele tri matrix "GG
right-hand side of Eq. (136), sin e the external opti al eld has no lo al- eld omponent.
It is important to distinguish the diele tri matrix "GG (q; ! ) from the diele tri fun tion
"(q; ! ). The diele tri fun tion "(q; ! ) is de ned by "(q; ! ) = Vext (q; ! )=Vtot;0 (q; ! ). When
lo al elds are disregarded, we have "(q; ! ) = "00 (q; ! ), but when lo al- eld e e ts are
in luded the diele tri fun tion is given by the inverse of the G,G0 = 0 omponent of the
inverse diele tri matrix:
h
i
"(q; ! ) = 1= "001 (q; ! ) :
(137)
For independent ele trons in the time-dependent Hartree or random phase approximation
(RPA) the diele tri matrix is that given in Se tion 5 in terms of the independent-parti le
polarizability P 0 :
4
0
A
(138)
"RP
GG (q; ! ) = GG
jq + Gj2 PGG (q; !);
0 (q; ! ) is given by the Adler{Wiser [80, 82 formula:
where PGG
0

0 (q; ! ) =
PGG
0

2
V

ii

hij exp(i(q + G)  r)ji0ihi0j exp( i(q + G0)  r)jii


!

fi (1 fi )
fi (1 fi )
;
+
"i "i + ! + i "i "i ! + i
0

(139)

whi h is an extension to in lude lo al- eld e e ts of the Ehrenrei h and Cohen formula for
the diele tri onstant in a solid [110.
In the s issors-operator approa h, the ondu tion-band energies in the denominator of
0 (q; ! ) are shifted by . Without lo al elds, the stati
the Adler-Wiser formula for PGG
sus eptibility , de ned by " = 1 + 4, is obtained by taking the limit q ! 0 in Eq. (138):
0 (q; 0)=q 2 .
 = limq!0 P00
0

90

within 5% of experiment. These good results are obtained in large part due to the parti ular approximations made to the band stru ture. For GaAs, Levine and Allan nd good
agreement with experiment by using the average GWA orre tion of 0.8 eV from the semirelativisti pseudopotential al ulation by Godby, S hluter and Sham [185. This orre tion
is added to a semirelativisti pseudopotential LDA bandstru ture (negle ting Ga 3d ore
relaxation and spin-orbit orre tions). Their LDA gap is 0.5 eV at the experimental latti e
onstant whi h yields a 1.3 eV gap after the s issors orre tion. This gap is 0.2 eV too small
ompared to experiment, but this underestimation of the gap is what is needed to get the
dominant ontribution from the strong peaks in the LDA absorption spe trum to end up
lose to the experimental peak stru tures.
For large band-gap materials (Egap >4 eV), GWA-based s issors-operator orre tions frequently lead to an underestimation of " that is as large as the overestimation by LDA. This
e e t was rst seen by Chen et al. for diamond and SiC [540. Table 36 shows the result
of Chen et al. for diamond, SiC and GaN. Here the LDA values again overestimate the
diele tri onstant but by only 4{6%. The average GWA orre tions to the dire t gaps are
of the order of 1{2 eV, whi h when used as s issors orre tions give diele tri onstants well
below experiment. Similar results are obtained by Adolph et al. [561 and by Gavrilenko
and Be hstedt [562, who on lude that to obtain an " in agreement with experiment a shift
of 0.5gap is needed in Si, 0.45gap in SiC, and 0.2gap in diamond.
Another important onsideration is the e e t on the opti al response of the quasiparti le
weight Z that multiplies the single-parti le Green fun tion (see Eqs. (7), (8), (18), and Se tion 11) Within the independent-quasiparti le approximation, the sus eptibility in Eq. (132)
above should be multiplied by the produ t of the ele tron and hole quasiparti le weights Z Zv
leading to a drasti redu tion of about a fa tor of two in the diele tri onstant [563, 564,
and even larger redu tions in higher-order response. In pra ti e, the multipli ation by Z Zv
is seldom made in opti al response al ulations, whi h a ounts for their su ess.
This pra ti e to disregard the redu tion due to quasiparti le weights has re ently been
put on a more solid foundation by the al ulations of Be hstedt et al. [564. They show that
when vertex orre tions in the form of ex itoni ele tron-hole intera tions are onsidered
the weight fa tor Z Zv is repla ed by a ombined weight fa tor Z v ' 0:9. Hen e the
orre tion due to Z and Zv is almost an eled by the e e t of vertex orre tions, whi h are
also negle ted in the GWA-based s issors-operator approa h. Figure 49 shows the imaginary
part of the diele tri fun tion of diamond and sili on obtained by Be hstedt et al. from LDA,
GWA with and without the Z Zv orre tion, and GWA plus vertex orre tions. A similar
an ellation between quasi-parti le weight and vertex orre tions for interband transitions
in metals was dis ussed by Beefermann and Ehrenrei h [151.
In summary, to hoose  from the gap mismat h leads to too large orre tions in most
materials, with in reasing error as the band-gap in reases. The on lusion is that we la k
a rst-prin iples method to hoose a orre t s issors shift. However, there is no doubt that
some s issors shift is needed, sin e the best LDA band stru tures yield gap values well below
the experimental gaps. Most authors today use a s issors shift in opti al response al ulations, but the method of hoosing the shift varies, and the shift is largely an empiri al way
89

gies and all wave fun tions un hanged [535, 536. That is, a term

Hs iss = 

j kih ; kj

(133)

is added to the LDA Hamiltonian. In the next se tion, we investigate the onsequen es of
adding su h a term to the LDA Hamiltonian. But we rst dis uss what value to hoose for
.
The dis ussion above on erning the band-gap problem suggests that one should hoose
exp E LDA . However, su h a hoi e often leads to an over orre tion of the too high
 = Egap
gap
LDA diele tri onstant. This over orre tion an be understood by onsidering the bandand k-spa e summations in Eq. (132).
The most important regions in k-spa e when al ulating " are those where valen e and
ondu tion bands are approximately parallel, leading to a large joint density of states. The
e e t of the joint density of states on the diele tri onstant is best seen when " is written
in terms of the imaginary part "2 (! ) via the Kramers-Kronig relation:
2 Z 1 "2 (! )
d!;
(134)
"=1+
 0 !
where
8 2 X
"2 (! ) =
jh
kjxjv kij2 (" k +  "vk ! ):
(135)
V ;v;k
The position matrix elements are the same in LDA and in the s issors-operator approa h,
sin e the wave fun tions are the same by onstru tion. The only e e t of the s issors shift 
in the expression for "2 (! ) is that  is added inside the fun tion. As shown in Fig. 39 in
Se tion 24 and in Figs. 48 and 49, for most semi ondu tors the dominant stru ture in "2 (! )
is not the region around the band gap but onsists of a ouple of peaks a few eV higher up
in energy.
To shift the main peaks in "2 (! ) to their experimental positions requires a  smaller than
the gap mismat h. Due to both band-stru ture and many-ele tron e e ts, the mismat h
between the LDA and the experimental regions of strong opti al absorption is not related
to the band-gap mismat h in an obvious way. Figure 48 shows the results by Hughes and
Sipe [556 for GaAs and GaP. They use a s issors shift to t the LDA band gaps to the
experimental gaps whi h puts the dominant absorption peaks about 0.5 eV too high. As
dis ussed in Se tions 9b and 24, in lusion of ex itoni e e ts will strongly improve the
absorption spe trum in regards to both peak position and the peak heights [154, 155, 156,
474, 475, 476. A systemati rst-prin iples argument for what  to hoose is therefore hard
to nd, and the s issors-shift approa h must be onsidered to be largely empiri al.
Early al ulations nd good agreement with experiment by using LDA gaps plus an
averaged GWA orre tion for , whi h suggests a lose to ab initio method for opti al al ulations [535, 536. Table 35 shows the results of Levine and Allan for the diele tri onstant
of Si, Ge, GaAs, GaP, AlAs, and AlP. Leaving the dis ussion of lo al- eld orre tions to
the next se tion, we see that the s issors approximation brings the too large LDA values to
88

ommonly used s alar relativisti pseudopotentials typi ally give a gap of 0.4{0.5 eV in GaAs
(in luding a 0.1 eV spin-orbit orre tion), whi h is about 0.3 eV larger than a fully relativisti
all-ele tron al ulation. In ontrast to GaAs, the band-gap of sili on is not sensitive to the
level of approximation, whi h shows that sili on is not a good test ase for the evaluation of
a urate methods. Note also the large e e ts in Table 33 for Ge and GaAs from the negle t
of relativisti e e ts even for these relatively light atoms.
This emphasis on the level of approximations made is equally important when the general a ura y of the GWA is evaluated. Table 34 ompares the underestimation of the most
a urate LDA gaps (di eren e between the last two olumns in Table 33) with the gap
orre tions from various approximate GWA s hemes: rst-order perturbation theory; self onsistently up-dated band energies; and in lusion of ore-polarization. The most a urate
values (last olumn) show that GWA orre tions in luding ore polarization e e ts added
onto fully relativisti , all-ele tron LDA energies do indeed ome within 0.1 eV of experiment.
However, other levels of approximation yield di erent on lusions. For example, pseudopotential al ulations that negle t spin-orbit intera tions (Table 33, olumn 2) ombined with
perturbative GWA orre tions (Table 34, olumn 2), whi h are ommonly used, typi ally
underestimate the band gap by 0.1-0.3 eV for Si, Ge, and GaAs.
The use of LDA theoreti al latti e onstants al ulated within a pseudopotential approximation an yield gaps half an eV larger than the gaps obtained at the experimental latti e
onstant. For example, one al ulation [552 found a gap of 1.0 eV in GaAs with a theoreti al latti e onstant obtained with a s alar relativisti pseudopotential. That approa h gave
a 1.7% too small latti e onstant (5.55 
A) whi h generated a 0.5 eV in rease in the LDA
band gap ompared to al ulations at the experimental latti e onstant (5.65 
A). Similarly,
Fiorentini [553 nds that the band gaps at the theoreti al latti e onstant from pseudopotential al ulations are in reased by 0.02 eV in Si, 0.45 eV in Ge, 0.61 eV in GaAs, and 0.27
eV in AlAs ompared to gaps obtained at the experimental latti e onstants.
Su h large overestimations of the LDA band gap an lead to the on lusion that LDA
gaps are good enough without self-energy orre tions. However, su h a laim is ountered
by the fa t that fully-relativisti LDA all-ele tron al ulations give latti e onstants in mu h
better agreement with experiment and mu h smaller gaps. For example, Alouani and Wills
[546 obtained a theoreti al latti e onstant in GaAs of 5.62 
A and a dire t gap of 0.29 eV.
Therefore, on lusions on erning the need for quasiparti le orre tions based on pseudopotential al ulations at the theoreti al latti e onstant must be onsidered with s epti ism.
The in lusion of gradient orre tions (GGA) to LDA does not alter this on lusion, although
GGA typi ally overestimates the latti e onstant [554, 555.
30. THE \SCISSORS OPERATOR" AND ITS LIMITATIONS
Ideally, one would like to add an energy- and momentum-dependent self-energy to the denominator in Eq. (132), but this is in general too omputationally ostly. An often used
simpli ation, alled the `s issors-operator approa h,' is to add a onstant, energy- and
momentum-independent shift  to the ondu tion-band energies, leaving the valen e ener87

sus eptibilities  and (2) are de ned by


P

=   E + (2)  EE;

(131)

where E is the total internal ele tri eld. The s alar produ t symbolizes the fa t that
in general the sus eptibilities are tensors. However, in many ommon materials only a
few tensor omponents are independent. In parti ular, for rystals with ubi symmetry
 = xx = yy = zz are the only non-zero omponents. We use a simple s alar notation for
all tensor properties below, and, only when needed do we add expli it fun tional dependen ies
on time, position, frequen y, or momentum.
In an insulator with ubi symmetry, the linear sus eptibility, in the independent-parti le
approximation, an be written as (V is the total volume) [538:
4 X jh kjxjv kij2
;
(132)
=
V ;v;k " k "vk
where ; v represent summations over ondu tion and valen e bands, k a summation over
the rst Brillouin zone, and " ;v are the orresponding single-parti le energies. The matrix
element is of the position operator x in some dire tion in real spa e.
Any ele troni band stru ture an be used in Eq. (132), but the most ommon hoi e is an
LDA band stru ture. Another possible hoi e would be, for example, one based on empiri al
pseudopotentials [539, for whi h the pseudopotential parameters have been adjusted to
reprodu e an experimental band stru ture. Sin e this hapter fo uses on the in uen e of
GWA self-energy orre tions in opti al response, we assume LDA wave fun tions throughout.
A major problem with LDA al ulations of the diele tri onstant " = 1 + 4 is the
underestimation of the band gap. It leads to a roughly equal relative overestimation of 
and therefore ", as shown in Fig. 47. However, in these sp-bonded materials the error
due to the use of LDA wave fun tions seems less severe. A on lusion supported by the
fa t that GWA al ulations give reasonable orre tions to the gap without hanging the
wave fun tions dramati ally. For higher-order response, the error due to the too small gap
be omes even worse, sin e for ea h order the power of the energy di eren es in reases by one
in the denominator of the formulas for the response oe ients. Hen e, the primary fo us in
opti al-response theory of semi ondu tors over the last few de ades has been on the best way
to orre t the LDA band gap without worrying about hanges to the wave fun tions. But
before dis ussing how gap orre tions an be introdu ed with a reasonable omputational
e ort, we want to dis uss in some detail how large the LDA error a tually is.
When the results of a parti ular publi ation are onsidered, it is important to note
exa tly how the LDA bandstru ture was obtained. In Table 33, we show for Si, Ge, and
GaAs how di erent approximations a e t the LDA gap. The table shows, from left to right,
the importan e of s alar relativisti e e ts with frozen ore states, spin-orbit intera tions
(fully relativisti ), and relaxation and hybridization of ore states. In GaAs, all these e e ts
are important if we aim at an a ura y of 0.1 eV for band-gap predi tions. With a 1.5
eV band gap, a 0.1 eV error orresponds to a 5{10% error in the diele tri onstant. The
86

VI. GWA al ulations and opti al response


For semi ondu tors and insulators, the lessons learned from the GWA regarding the band
stru ture have led to a new level of a ura y in al ulations of opti al response. The reason
is the ru ial role played by the band gap in determining the opti al polarizability of non ondu ting materials. E orts to orre t the too small LDA band gaps are therefore dire tly
onne ted to e orts to a urately al ulate opti al response { diele tri onstant, opti al
absorption, se ond-harmoni generation, et . In Se tion 29, we dis uss in detail the overestimate of opti al onstants in LDA al ulations, and in Se tion 30 we introdu e the widely
used s issors-operator approa h [535, 536. In this approa h the self-energy orre tions to the
LDA band stru ture are approximated by a rigid shift of all the ondu tion-band energies,
while the valen e-band energies are una e ted.
The inhomogeneous ele tron density in rystalline materials generates ele tri elds that
vary over distan es of the order of the latti e onstant. These so- alled lo al elds [80, 82
must be onsidered when a urate al ulations of opti al response are performed. Typi ally,
as shown below, the lo al- eld e e ts are of order 5{10% in the diele tri onstant and 1030% in the se ond-harmoni oe ient. In Se tion 31, we outline the theory of lo al- eld
e e ts in opti al response and review the numeri al results for a range of semi ondu tors
and insulators.
Finally, in Se tion 32 we dis uss the possibility of obtaining orre t opti al response oef ients from density fun tional theory without the introdu tion of quasiparti le orre tions.
Re ent work by Gonze, Ghosez, and Godby [537 suggests that previous opti al response al ulations have negle ted an important ex hange- orrelation e e t spe i to systems with
a band gap. The Kohn-Sham ele trons are a ted upon not only by the physi al ele tri
eld { the external opti al eld plus the indu ed Hartree eld { but also by a titious
eld derived from the indu ed hange in the ex hange- orrelation potential. This titious
ex hange- orrelation ele tri eld ountera ts the unphysi al Kohn-Sham energy spe trum
so as to produ e the orre t indu ed density or polarization.
The dis ussion below has some overlap with the previous dis ussion on erning the al ulation of the diele tri matrix for use in GWA al ulations. However, the fo us is di erent.
Previously, we were on erned only with methods to obtain a diele tri matrix suitable for
al ulations of the s reened Coulomb intera tion in the GWA. In parti ular, a prominent
role was played by the need to perform an integration over all frequen ies (see Eq. (35)). In
the dis ussion below, we are on erned with ways to al ulate opti al response oe ients
with high a ura y (within 5% of experiment). In parti ular, we dis uss al ulations of the
linear and nonlinear ele tri sus eptibilities in the long-wavelength limit.
29. OVERESTIMATION OF OPTICAL CONSTANTS WITHIN DFT
In terms of the indu ed ma ros opi polarization density P, the linear and se ond-order
85

[532

Vlo (r) =

(r; r0 ; E ) (r0)dr0 = (r):

(130)

For an Al(111) surfa e Fig. 45 shows that (i) outside the metal surfa e, Vlo (r) has the orre t
asymptoti , image-like behavior, and (ii) inside the metal surfa e, self-energy orre tions to
LDA for states lose to the Fermi energy are small resulting in nearly identi al values of
Vlo (r) and Vx LDA (r).
Essential for the above su essful appli ations of the dynami ally s reened intera tion
approximation is a self- onsistent evaluation of quasiparti le states [499. The di eren e
between the exponential LDA de ay and the GWA inverse power law de ay leads to an in reased weight of the quasiparti le states in the near-surfa e region whi h is demonstrated
in Fig. 46. Note that similar results as the ones dis ussed here for the Al(111) surfa e have
been obtained earlier than those of Ref. [499 by Deisz, Eguiluz, Hanke, and ollaborators
[532, 533, 534 for the ase of a jellium surfa e. This work is reviewed in Ref. [14.

84

luster an be reasonably well des ribed by an e e tive one-parti le, spheri al potential. The
properties of the metal lusters { su h as their total energy and hen e their stability, their
ionization potential, and their ele tron anity { hange in an abrupt way whenever one
shell of ele trons is lled up, leading to an abrupt hange as a fun tion of luster size. The
spheri al, one-parti le potential of hoi e is the so- alled jellium-sphere-ba kground model
in whi h the positive ion ores in the luster are repla ed with a onstant density sphere.
The sphere radius is given by rs N 1=3 with rs being the Wigner-Seitz radius orresponding
to the average metal density.
As shown in Fig. 44, LDA al ulations of the ionization potential and ele tron anity
do not re e t the experimental shell stru ture, i.e., the dependen e on luster size of these
quantities [522, 523. This dis repan y arises from LDA's in omplete an ellation between
the Hartree and ex hange self-intera tion { the so- alled self-intera tion error { and in reases
with de reasing system size whi h on eals the strong size dependen e in parti ular of the
ionization potential [522, 523. Self-intera tion errors lead to an underbinding of the o upied
and an overbinding of the uno upied states in strongly lo alized systems.
The size dependen e of the ionization potential and the ele tron anity are well des ribed in GWA due to the fa t that self-intera tion errors are small in standard GWA [524.
Remaining quantitative di eren es with experiment are attributed to the jellium-sphereba kground model and nite temperature e e ts [522, 523. The quasiparti le results for the
ionization potential are systemati ally above the orresponding LDA results and eliminate
the LDA underbinding of o upied states due to self-intera tion errors. Similarly, the absolute value of the GWA ele tron anity is below the orresponding LDA value sin e GWA
orre ts for the overbinding of uno upied states within LDA.
28. SURFACES
In lassi al ele trostati s, an ele tron at a lo ation z outside a metal surfa e indu es a
surfa e harge and in turn experien es an attra tive image potential Vim (z ) whose asymptoti
form for large z is given as 1=(4(z z0 )), where z0 is the e e tive edge of the metal.
On a mi ros opi level, the rearrangement of harges at the metal surfa e is due to longrange ex hange and orrelation e e ts whi h are absent in LDA due to the exponential,
rather than inverse power law, de ay of the LDA ex hange orrelation potential outside the
metal surfa e [525. This severe LDA failure leads to a poor des ription of surfa e states
and to an absen e of image states and resonan es in LDA. Dis repan ies between LDA
results and results of surfa e-sensitive experimental te hniques su h as low-energy ele tron
di ra tion [526, 527, s anning tunneling mi ros opy [528, 529, and inverse and two-photon
photoemission experiments [530, 531 are therefore expe ted.
The non-lo al, energy-dependent, many-body e e ts that ause the asymptoti inverse
power law behavior of the image potential are ontained in the GWA self-energy. To obtain a
lo al, state-dependent potential Vlo (r) from the non-lo al self-energy that an be ompared
with the lo al image potential and the LDA ex hange orrelation potential Vx LDA one de nes
83

self- onsisten y. This estimate suggests that all published results for w miss physi al effe ts that are as large as the di eren e between the Jensen{Lyo{Plummer experimental data
[505, 506 and nearly-free-ele tron theory [514. Consequently, a quantitative analysis and
uni ed physi al understanding of the Na photoemission experiments require further work,
in parti ular, the establishment of a onsistent set of vertex orre tions, self- onsisten y,
surfa e, and life-time e e ts [515.
. d and f ele tron metals
The LDA band stru ture of the transition metal Ni has four dis repan ies with experiment
[68: (i) the experimental 3d band width of 3.3 eV is about 30% smaller than its LDA value
of 4.5 eV, (ii) the experimental ex hange splitting of 0.25-0.30 eV is about half of the LDA
value, (iii) a 6 eV satellite in the photoemission spe trum is absent in LDA, and (iv ) the
bottom of the 3d band annot be des ribed by sharp LDA ex itations sin e these states
have quasiparti le widths of about 2 eV indi ating strong intera tions between 3d ele trons.
Quasiparti le al ulations of the d ele tron metal Ni and the f ele tron metal Gd an be
found in Refs. [68 and [516, respe tively, and are extensively reviewed in Ref. [14. Here,
the dis ussion is limited to a short des ription of the su esses and failures of GWA in the
ase of Ni [68.
Quasiparti le al ulations for Ni lead to a signi ant improvement of the LDA band
stru ture and in parti ular redu e the 3d band width by about 1 eV in agreement with
experiment. Experimental quasiparti le lifetimes are reprodu ed as well. Self-energy shifts in
Ni are strongly state dependent due to the fa t that the LDA ex hange- orrelation potential
is a better approximation for the self-energy of, for example, free-ele tron-like s states than
for the self-energy of strongly orrelated d states. The di erent hara ter of the s like and d
like states is also re e ted in the quasiparti le weight whi h is about 0.7 for s like but only
about 0.5 for d like states.
The 6 eV satellite is not reprodu ed in GWA and the ex hange splitting is only marginally
improved sin e both features result from strong hole-hole intera tions that require the in lusion of vertex orre tions. A ommon explanation of the photoemission pro ess starts with
the reation of a 3d hole whi h introdu es a strong perturbation due to its lo alized nature
and ex ites another 3d ele tron to an empty state just above the Fermi level. The two holes
s atter repeatedly and form a bound state at 6 eV. A rst-prin iples T-matrix al ulation
[71 in ludes the negle ted hole-hole intera tion via ladder diagrams and leads to a 6 eV
satellite and an improved ex hange splitting.
27. CLUSTERS
The total energy per atom of, e.g., Na lusters as a fun tion of the number of Na atoms
N , is a smooth fun tion ex ept for small kinks at N = 8, 18, 20, 34, et . (for a review
on metal lusters, see, for instan e, Ref. [517). This shell stru ture is reminis ent of the
behavior observed in nu lei and atoms and results from the fa t that the ele trons in the alkali
82

of Na via photoemission [505, 506 ontradi ts nearly-free-ele tron theory in two important
ways: (i) the measured band width is about 0.6 eV smaller than the nearly-free-ele tron
value of 3.2 eV, and (ii) sharp, non-dispersive peaks in the energy gap an be identi ed for
photon energies of about 35 eV, whi h peaks have no equivalent in nearly-free-ele tron theory. Self-energy orre tions in GWA for jellium at rs = 3:95 (average density of Na) narrow
the band width by only 0.3 eV raising on ern about the validity of GWA for this simple,
weakly orrelated solid. Several improvements and extensions to GWA are onsidered in
the literature whi h all reprodu e experimentally observed w's but orrespond to di erent
physi s. Di eren es between these approa hes have been dis ussed in Se tion 14. Here, we
give a short summary of the basi assumptions and results of the di erent te hniques.
Self-energy e e ts and surfa e-indu ed momentum-non- onserving ex itations a ount
ea h for about half of the observed Na band-width orre tion [229, 241, 265. The latter
e e t also provides a possible explanation for the experimentally observed non-dispersive
peaks around 35 eV in the photoemission spe trum shown in Fig. 43. The in lusion of surfa e
e e ts is important a ording to the work of Mahan, Shung, and Sernelius [229, 241, 265
sin e the mean free path of the photoele trons is only 5-6 
A in Na, i.e., photoele trons probe
only the rst two to three layers of the material. Mahan et al. use Rayleigh-S hrodinger
perturbation theory { suggesting that it is more a urate than GWA for alkali metals { and
the surfa e potential by Lang and Kohn [507 (see Se tion 14).
A \best G, best W " approa h that goes beyond standard RPA-based GWA al ulations
by (i) in luding LDA vertex orre tions in the diele tri s reening but not in the self-energy,
and (ii) determining the quasiparti le energies self- onsistently, leads to agreement between
theoreti al and experimental band widths [184, 257, 258 as shown in Table 32. Point (i)
alone leads to a band width redu tion of 0.57 eV in Na, point (i) and (ii) together lead
to a band width redu tion of 0.71 eV ompared to a standard GWA value of 0.31 eV and
redu e the band width from the LDA value of 3.16 eV to 2.45 eV [511. This approa h does
not address the existen e of a nearly dispersionless peak in the photoemission spe trum.
Northrup et al. [184, 257, 258 motivate the in lusion of vertex orre tions in the s reening
in terms of a better ful llment of a Ward identity related to harge onservation [156. Their
approa h is in ontradi tion with the arguments of Mahan [10 and others [266.
Results of partially self- onsistent GWA al ulations of the band-width redu tion for
jellium [232 an be extended to alkali metals and give good agreement with experiment
if (i) stati vertex orre tions similar to the Hubbard lo al- eld fa tor are in luded in the
diele tri fun tion, and (ii) dynami al vertex orre tions to se ond-order in the s reened
intera tion W are in luded in the self-energy. In ontrast to Mahan [10, Shirley suggests
that a dynami al vertex orre tion to the self-energy in onjun tion with a stati vertex
orre tion in the s reening is more appropriate [512 for the determination of w. Results
of Shirley's al ulation [513 are given in Table 32.
Estimates based on the partially and fully self- onsistent GWA al ulations shown in
Fig. 19 for the band-width redu tion w of jellium at rs = 4 suggest that (i) non-self onsistent results for w in rease by about 0.7 eV upon in lusion of self- onsisten y, and
(ii) partially self- onsistent results for w in rease by about 0.4 eV upon in lusion of full
81

V. Metals
Quasiparti le al ulations for metals have been reported for bulk (Se tion 26), lusters (Se tion 27), and surfa es (Se tion 28) and are reviewed in detail in Ref. [14. This hapter
on entrates on a few important aspe ts su h as the importan e of ore-valen e ex hange for
the energy-dependen e of the self-energy, the band width of alkali metals, and quasiparti le
orre tions in Ni, and the reader is referred to Ref. [14 for a more detailed dis ussion of
some of the quasiparti le appli ations. In parti ular, regarding surfa es, we dis uss only the
re ent work of White et al. [499 on an Al (111) metal surfa e sin e the extensive work on
jellium surfa es has been reviewed in Ref. [14.
26. BULK
a. Core-valen e ex hange

Inverse photoemission spe tra of transition and noble metals for energies up to 70 eV above
the Fermi energy EF show peaks that an be identi ed with similar stru tures in a LDA
density of states [500. However, for energies larger than about 10 eV the theoreti al peak
positions underestimate experiment by an amount that grows linearly with energy (prefa tor
of about 0.05 to 0.10, Ref. [500). Sin e GWA self-energy orre tions within the jellium model
de rease as the inverse square root of the energy E rather than in rease linearly with E ,
improvements beyond the jellium model must be onsidered [132, 501.
The non-lo al ex hange intera tion between valen e ele trons (e.g., 5s ele trons in Ag)
and ele trons in losed shells (e.g., the 4s, 4p, and 4d ele trons in Ag) is negle ted in jelliumbased GWA al ulations even though it ontributes about 1-10 eV to the ondu tion band
ele tron self-energy for the Ag 5s ele tron [216 as shown in Fig. 41. As shown both in
Fig. 41 and Fig. 42, nonlo al ex hange of the Ag 5s ele tron with the Ag 4s, 4p, and 4d
ele trons [216 is essential to obtain qualitative agreement with experiment and leads to a
self-energy that (i) is approximately onstant for E  10 eV, (ii) in reases linearly with
energy for 10 eV  E  70 eV, and (iii) de reases as E 1 for E  70 eV [216. More
than qualitative or semi-quantitative agreement with experiment annot be expe ted sin e
Ref. [216 models (i) diele tri s reening by tting the experimental ele tron energy loss
fun tion Im[1="(q = 0; ! ), (ii) the dispersion of plasmon poles, and (iii) the 4s, 4p, and 4d
ele trons using atomi Roothaan{Hartree{Fo k wave fun tions [502, 503.
b. Alkali metals
The weakness of the e e tive rystal potential in alkali metals seems to permit a nearlyfree-ele tron-model [504 des ription of the ondu tion ele trons and seems to o er an experimentally a essible system whose many-body orre tions are (i) weak, allowing the use
of perturbation theory su h as GWA, and (ii) not ompli ated by the e e ts of a omplex
band stru ture. However, the experimental determination of the o upied band width w
80

dimensional trans-polya etylene (trans-(CH)x ) [488 { the simplest prototype of a ondu ting
polymer { and a quasi-two-dimensional hypotheti al polysilane ompound [489. The polysilane ompound onsists of planar Si layers sta ked in the (111) dire tion and terminated by
hydrogen. Repla ement of 50% of all hydrogen in polysilane by OH groups gives siloxene,
a ompound suggested to be responsible for visible lumines en e in porous sili on [490.
These al ulations are dis ussed below. Cal ulations on BN sheets have been mentioned in
onne tion with the quasiparti le al ulations of solid C60 (see Se tion 19 ).
Trans-polya etylene. In trans-(CH)x [488, GWA leads to a 68% redu tion of the initial Hartree-Fo k band gap of 5.83 eV to predi t a gap of 1.86 eV in good agreement with
the experimental range of gap energies from 1.4 to 1.8 eV [491, 492, 493, 494, 495, 496.
This statement holds only if quasiparti le energies are determined self- onsistently. Self onsisten y in the quasiparti le energies is ne essary to a hieve quantitative agreement with
experiment, sin e the rst iteration redu es the Hartree-Fo k gap only to 3.1 eV [488. The
theoreti al ele tron-energy-loss spe trum shows a low-energy plasmon peak whose lo ation
and linear dispersion with respe t to the re ipro al wave ve tor k agree well with experiment
[492, 495, 496. A se ond plasmon peak at 13.2 eV deviates signi antly from the experimental peak at 22.5 eV. This dis repan y may be due to the limited Gaussian basis set
used in Ref. [488 whi h annot des ribe high energy states a urately and to experimental
di ulties related to the produ tion of high quality rystalline trans-(CH)x [488.
Polysilane. A two Si-layer polysilane ompound [489 exhibits strong quantum on nement e e ts with strong quasi-dire t opti al transitions. The dire t GWA gap at equals
3.0 eV and is only 0.2 eV larger than the indire t gap. Self-energy orre tions of 0.9 eV are
a substantial fra tion of the band gap. Siloxene is formed by substitution of OH for H for
50% of all hydrogen atoms in the planar polysilane. Siloxene has a dire t quasiparti le gap
of 1.70.3 eV [489 with strong opti al transitions [497. The siloxene band gap orresponds
reasonably well to emission in the red, whi h emission is observed in porous sili on [498.

79

in smaller, few tenths of an eV, hanges in the nal ex itation energies [282.
25. ATOMS AND MOLECULES
This se tion des ribes quasiparti le al ulations of atoms and mole ules. Atoms are appli ations of GWA to \zero-dimensional" systems. GWA al ulations for mole ules have only
been reported for quasi-one-dimensional and quasi-two-dimensional systems. To understand
whether GWA aptures the most important physi s of these systems also gives important
insights into the usefulness of quasiparti le al ulations in strongly orrelated solids su h
as NiO and high-T uprates where orrelations are often strongly lo alized, i.e., \atomi like." Extensions to quasiparti le al ulations to in lude vertex orre tions that are valid
for atoms and mole ules may therefore be of relevan e for solids and are the fo us of this
se tion. Other aspe ts, su h as the physi s of ore-valen e orrelations in atoms and their
relevan e for solids have been dis ussed in Se tion 12.
a. Atoms
Assessment of the usefulness of GWA for atoms requires the omparison of theoreti al and
experimental results for some key quantities su h as the rst and se ond ionization potentials
and transfer energies [67. The GWA ionization potentials of major group elements su h as
B, Al, and Ga deviate on average only 3% from experimental values, ompared to a 12%
deviation in Hartree-Fo k [67. No systemati improvement ompared to the lo al spin
density approximation (LSDA) [481, 482 is obtained. For s ! p promotion energies the
error is 20% in GWA, 40% in Hartree-Fo k, and 5% in LSDA as shown in Table 31. In
absolute terms, deviations between GWA and experiment vary between 0 and 0.8 eV. Hen e,
taking the dynami ally s reened intera tion into a ount leads to a signi antly improved
agreement with experiment ompared to Hartree-Fo k but not ompared to LSDA. Absolute
errors ex eed hemi al a ura y by more than one order of magnitude [67.
Figure 40 shows the s ! d promotion energy in the iron series and demonstrates [67, 485
that (i) GWA agrees with experiment quantitatively for the rst half of the iron series in
ontrast to Hartree-Fo k and the LSDA, (ii) GWA reprodu es experimental trends qualitatively for the se ond half of the iron series in ontrast to Hartree-Fo k but is inferior by
about a fa tor of three to the LSDA, and (iii) GWA annot ompete in a ura y with the
results of a s reened-ex hange lo al spin density approa h [487 for the entire iron series. The
breakdown of GWA for the se ond half of the iron series stems from the formation of strongly
orrelated pairs of ele trons with opposite spin [67. These strong, lo alized two-body orrelations are not in luded in the standard dynami ally s reened intera tion approximation,
and their in lusion would require vertex orre tions.
b. Mole ules
Besides \zero-dimensional" atoms, quasiparti le al ulations have been done for quasi-one78

tions. Note that LDA al ulations for solid, mole ular hydrogen are di ult [457 sin e (i)
the exa t experimental stru ture at metallization is unknown, (ii) the large zero-point motion energy of the H2 mole ules makes a urate total energy al ulations di ult sin e it is
larger by an order of magnitude than the di eren es in ele troni energies between di erent
mole ular orientations, and (iii) in ontrast to the total energy the minimum band gap is
very sensitive to the orientation of H2 mole ule vibration. Disorder in the vibration dire tion
of the H2 mole ules in reases the minimum band gap and is (i) negligible at zero pressure
[469, and (ii) ru ial at high densities exempli ed by a metal-insulator transition pressure
of 151 GPa for h p H2 whose mole ules are prefe tly aligned along the -axis and of 300
GPa for orientationally disordered H2 [457. Experimentally, metallization of solid hydrogen
{ de ned by a nite T ! 0 DC ondu tivity { remains to be observed [470, 471, 472, 473.
Opti al experiments have failed to dete t eviden e for gap losure below about 200 GPa
[470, 471 and a metal-insulator transition pressure of more than 300 GPa seems likely [473.
24. EXCITONS
Intera ting ele tron-hole pairs are reated in absorption spe tros opy and their ele tronhole attra tion leads to the following modi ations of the opti al absorption spe tra of
semi ondu tors and insulators: (i) the energies of low-lying ex ited states are de reased,
and (ii) the orresponding os illator strength is in reased. Semi-empiri al tight-binding
results of Hanke, Sham, and ollaborators (see Se tion 9 b) for Si show about an eV shift of
the energies of low-lying ex ited states to lower energies and an os illator strength in rease
of the E1 peak at about 3.5 eV by 50% in good agreement with experiment. However, the
strength of the theoreti al E1 peak is predi ted to be larger than that of the 4.2 eV E2 peak
in ontrast to experiment.
Re ent implementations that in lude ex itoni orrelations extend the Hanke-Sham approa h by using rst-prin iples rather than semi-empiri al wave fun tions and band energies.
Appli ations to bulk semi ondu tors and wide-gap insulators (Si, Ge, GaAs, diamond, Li2O,
MgO, LiF; Refs. [56, 474, 475, 476, 477) on rm Hanke's and Sham's on lusions regarding
the shift of low-lying ex ited states to lower energies and nd in addition the orre t ordering (E1 < E2 ) of the two main peaks in the Si absorption spe trum. Figure 39 ompares
theoreti al absorption spe tra of Si and diamond with and without ex itoni orrelations
with experimental results [474, 475 and shows that (i) good agreement between theory and
experiment is obtained, and (ii) ex itoni e e ts are more important in large-gap insulators
than in small- and medium-gap semi ondu tors, sin e s reening is less e e tive in the former.
Core-hole ex itons have been studied in LiF, NaF, KF, graphite, diamond, and h-BN [479.
Ex itoni binding energies in lusters su h as Na4 (Ref. [480) or Sin Hm (Ref. [282)
amount to a few eV ompared to binding energies of a few meV in bulk, sin e (i) s reening
is ine ient ompared to the bulk, and (ii) ele trons and holes are on ned in a small region. In ontrast to bulk ex itons, whi h at low energies an be des ribed by singly ex ited
ele troni states, ex itons in lusters require the onsideration of several ex ited ele troni
states [282, 480. Note also that dynami s reening of the ele tron-hole intera tion results
77

[456, 457, solid mole ular hydrogen [457, 458, and diamond [459. Other possible s enarios
for metal-insulator transitions in lude stru tural transformations as is the ase for Si under
pressure [460 and simultaneous magneti and metal-insulator transitions as in NiI2 [461. To
date, quasiparti le al ulations for stru tural or magneti metal-insulator transitions have
not been attempted.
The simplest estimate of the metal-insulator transition pressure, at whi h band overlap
o urs, is given by the negative ratio of the energy gap Egap and the variation of the energy
gap with respe t to pressure, dEgap =dP . Assuming linear behavior, a theory that predi ts
Egap and dEgap =dP in agreement with experiment will predi t orre t transition pressures.
Table 30 indi ates that the derivative of energy gaps with respe t to pressure evaluated at the
equilibrium volume is rather well des ribed in LDA. The su ess of LDA in the determination
of dEgap =dP an be understood in terms of a simple two-band semi ondu tor model [465
whi h shows that (i) the s reened ex hange term is not very sensitive to pressure, and that
(ii) the dependen e of the self-energy on the density and hen e on pressure is mainly due to
its Coulomb hole term. The Coulomb hole term an be approximated by a lo al potential, for
instan e an LDA ex hange- orrelation potential (see Se tion 10). Note that, with dEgap =dP
being rather well des ribed in LDA, the LDA band gap underestimation leads to a systemati
underestimation of the metal-insulator transition pressure.
The in reased band gap in GWA al ulations ompared to LDA leads to a higher transition pressure in better agreement with experiment. For example, the transition pressure
of solid Xe [457 is 128 GPa in omparison to 104 GPa in LDA and experimental values of
1325 GPa [466 and 150 GPa [467. Note that spin-orbit oupling must be taken into a ount in the al ulations [457. An LDA al ulation without spin orbit predi ts a transition
pressure of 123 GPa and hen e agrees with experiment although it does not des ribe the
physi s orre tly. The high-pressure behavior of diamond is of parti ular interest due to the
wide spread use of diamond-anvil ells. In diamond, the minimum band gap de reases under
appli ation of anisotropi pressure along the [001 dire tion and the pressure oe ient for
the minimum gap is very sensitive to the degree of anisotropy of the stress [459. The experimental geometry and hen e the stress anisotropy in diamond-anvil ells is not fully known,
whi h may explain the underestimation of the experimental diamond metallization pressure
of 700-900 GPa [468 by GWA al ulations [459 that predi t a metallization pressure of 400
GPa for an idealized geometry.
The self-energy orre tion to the LDA band stru ture of solid mole ular hydrogen shows
a non-linear density dependen e and is larger for mole ular hydrogen at equilibrium than
for mole ular hydrogen under large pressure (at high densities) [457. Figure 38 depi ts the
density dependen e of the band gap of solid mole ular hydrogen for LDA, Hartree-Fo k,
and GWA. For low densities (atmospheri pressure) the self-energy orre tion to LDA is
large sin e this regime is dominated by ex hange and GWA is lose to Hartree-Fo k whi h
is known to be a urate for mole ular solids. For high densities, i.e., large pressures, the
ele tron density of solid mole ular hydrogen be omes more uniform and onsequently the
orre tions to LDA be ome smaller. Sin e the orre tions to the LDA band stru ture are
non- onstant, it follows that dEgap =dP will be di erent in LDA and quasiparti le al ula76

22. DEFECTS
Defe ts in semi ondu tors a e t the transport, ele troni , and opti al properties by introdu ing defe t levels within the band gap. An LDA des ription of defe t levels is insu ient sin e
(i) the underestimation of the bulk band gap by 30-100% translates into a orresponding
un ertainty for the defe t level position, and (ii) quasiparti le shifts depend on the hara ter of the defe t level and annot be estimated from the shifts of the bulk band edges in a
simple way. Indeed, we have dis ussed examples of strongly dispersive and state-dependent
quasiparti le shifts at semi ondu tor surfa es, in transition metals, and even in large gap
bulk insulators (Se tions 18, 19, 20, 21, and 26).
Quasiparti le al ulations an determine defe t levels a urately but are omputationally
hallenging. To date, appli ations are limited to the F- enter defe t or halogen va an y in
LiCl [455 and an oxygen va an y in zir onia, ZrO2 [57. We on ne the dis ussion to the
halogen va an y in LiCl sin e this system is an ele troni ally and stru turally simple point
defe t. This neutral va an y ontains one bound ele tron in a highly lo alized (within one to
two latti e onstants) 1s state and shows stru tural relaxations relative to the ideal rystal
stru ture that are mostly on ned to nearest-neighbor alkali-metal atoms [455. In this ase,
a theoreti al des ription of the F- enter using a super ell approa h with relatively small unit
ells seems appropriate.
The fundamental ele troni F- enter transitions are (i) transitions from the lo alized 1s
ele tron to the ondu tion band riti al points at L, , and X , and (ii) an intra-defe t
transition from the lo alized 1s to a lo alized 2p level. For (i), the experimental values
of 4.5 eV, 5.0 eV, and 5.8 eV for the L, , and X transitions are well reprodu ed by the
quasiparti le values 4.5 eV, 5.0 eV, and 5.7 eV whi h orre t LDA results of 1.8 eV, 2.2 eV,
and 2.8 eV by an almost onstant shift of 2.8 eV [455. For (ii), due to the lo alized nature
of the 1s and 2p orbitals involved in the 1s ! 2p intra-defe t ex itation, ex itoni e e ts
must be in luded in the determination of the quasiparti le transition energy. These e e ts
lower the transition energy by about 1 eV leading to a quasiparti le value of 3.4 eV { a 1.0
eV orre tion to the LDA value of 2.4 eV { in good agreement with experiments ranging
from 3.1-3.3 eV [455.
Besides ex itoni e e ts, quasiparti le defe t al ulations are hallenging due to problems
related to nite size e e ts, the treatment of the lo alization and spin of the defe t ele tron,
the possible need for a self- onsistent treatment of quasiparti le defe t states, et . In the
ase of the 2p defe t state even the determination of the orresponding LDA state is di ult
sin e the band gap underestimation in LDA auses this state to be resonant and hybridize
with bulk bands. For a detailed dis ussion of te hni al problems o urring in GWA defe t
al ulations we refer the reader to Ref. [455.
23. PRESSURE
Quasiparti le al ulations an des ribe isostru tural metal-insulator transitions due to pressureindu ed overlap of ondu tion and valen e bands. Examples dis ussed below in lude solid Xe
75

de rease the surfa e-state dispersion as shown by the following examples. For the Ge(111):As
(11) surfa e [428, 432 quasiparti le orre tions in rease the band width of the o upied
As lone pair band by 0.5 eV (LDA 1.18 eV, GWA 1.64 eV) in ex ellent agreement with
experiment (1.62 eV, Ref. [433, 434, 435) and modify the unphysi al, at LDA dispersion into
a paraboli dispersion at  in the surfa e Brillouin zone as shown in Fig. 35. For the Si(111):H
(11) surfa e [429, 436 the o upied surfa e band a0 between M and K has an LDA band
width of 0.42 eV but none in GWA and experiment. Note that unre onstru ted (11)
surfa es that result from passivation with As or H are ex ellent systems for quasiparti le
al ulations sin e (i) the ompli ations of surfa e re onstru tions are eliminated, and (ii)
super ell al ulations an be based on a small 11 unit ell rather than 21, 42, or even
larger unit ells.
Quasiparti le al ulations bring the alignment of o upied states with respe t to the
valen e band maximum into agreement with experiment. Large self-energy orre tions of
0.5 to 0.8 eV of o upied surfa es states are obtained for strongly lo alized surfa e states
of the Si(111):H (11) surfa e and are shown in Table 29. Strongly lo alized LDA states are
underbound sin e the Hartree and ex hange self intera tions an el only partially in LDA.
These self-intera tion errors are largely eliminated in GWA leading to the large self-energy
orre tions mentioned above.
GWA al ulations annot always eliminate the dis repan ies between LDA and experiment in the dispersion and position of o upied surfa e states. A ase in point is the free
Ge(001) (21) surfa e [437 whose band stru ture is shown in Fig. 36. Two on lusions
follow from Fig. 36: (i) a signi ant dis repan y of up to 0.8 eV remains between quasiparti le al ulations and experiment along the JK/2 to J0 dire tion in the surfa e Brillouin
zone, and (ii) the 0.6 eV experimental band width of the Ddown state is strongly overestimated in quasiparti le theory ( 1.0 eV, Ref. [437). Similar dis repan ies exist for the
sulphur-terminated Ge(001):S (21) surfa e [437. Here the energies of the o upied quasiparti le D surfa e band and the o upied B surfa e band are underbound by 0.9 and 0.4
eV, respe tively, ompared to experiment.
Quasiparti le al ulations for surfa e states help understand and analyze surfa e re onstru tions and an be espe ially valuable when LDA total energy minimizations lead to
ontradi ting results with very di erent ele troni properties. For example, the Pandey
 -bonded- hain model is favored for the explanation of the C(111) (21) surfa e re onstru tion but the pre ise position of the atoms in the surfa e has been a subje t of dis ussion.
Vanderbilt and Louie [443 suggest a surfa e geometry of slightly bu kled but undimerized
hains based on a linear- ombination-of-atomi -orbitals LDA al ulation. Iarlori et al. [444
nd a dimerized surfa e with no bu kling based on LDA mole ular dynami s simulations.
Model GWA al ulations by Kress, Fiedler, and Be hstedt [445, 446 whose results are shown
in Fig. 37 support the dimerized model. The quasiparti le al ulations show that (i) the
Vanderbilt{Louie model leads to a metalli surfa e and (ii) the model by Iarlori et al. opens
up a surfa e gap of 1.70.3 eV in good agreement with the experimental value of about 2.0
eV [447, 448.
74

and ondu tion band as in the lassi al ase [425, 426.


21. SURFACES
The theoreti al determination of surfa e stru tures and re onstru tions relies on two te hniques [428: (i) al ulation of surfa e-state bands for proposed surfa e geometries and omparison with spe tros opi data, and (ii) total energy minimization over some set of geometries to nd optimal positions for atoms near the surfa e. While the se ond approa h is a
reliable tool due to the a ura y of LDA in determining densities, the rst approa h su ers
from the LDA band-gap underestimation whi h translates into similar albeit smaller errors
for surfa e states. Reliable empiri al orre tions to LDA are di ult to onstru t sin e
quasiparti le orre tions for surfa e states an show strong dispersion rather than simple
\s issors-shift"-like behavior as is dis ussed below.
LDA surfa e-state energies disagree with experiment [428 sin e (i) band gaps between
empty and o upied surfa e-state energies are too small, (ii) the dispersion of LDA surfa e
band states is too small in some ases, too large in others, and (iii) the pla ement of o upied
surfa es state energies is in some ases too high by 0.5 to 1.0 eV relative to the bulk valen e
band maximum. Two missing physi al e e ts must be onsidered to improve upon these
LDA failures [428. First, the in lusion of lo al elds in the diele tri matrix is ru ial for the
quasiparti le approa h sin e these lo al elds des ribe the strongly inhomogeneous s reening
(bulk like vs. va uum) at the surfa e. Se ond, the non-lo ality of the self-energy operator is
more sensitive to the lo alization properties of surfa e states than the only density-dependent
LDA. This non-lo ality leads to a modi ed dispersion of the quasiparti le energies throughout
the surfa e Brillouin zone.
Quasiparti le orre tions to the LDA surfa e band gap lead to improved agreement with
experiment and depend strongly on the hara ter of the o upied and uno upied surfa e
states [429. The o upied and uno upied surfa e states of the GaAs(111) (21) surfa e
[430 derive their hara ter from the orresponding bulk valen e and ondu tion bands and
are lo alized on the As and Ga atoms, respe tively. Consequently, the quasiparti le orre tions to the surfa e states are substantial and amount to a roughly rigid shift by 0.7 eV of
the uno upied surfa e states with respe t to the o upied surfa e states, whi h leads to a
quasiparti le surfa e gap of 2.0 eV [430 in good agreement with the experimental value of 1.9
eV [431. The quasiparti le orre tions for surfa es states of the Ge(111):As (11) [428, 432
surfa e are di erent from the bulk orre tions for Ge valen e and ondu tion bands sin e (i)
the o upied surfa e state is an As lone pair, i.e., a lled As dangling bond, and not derived
from bulk Ge states, and (ii) the uno upied surfa e states derive their hara ter both from
Ge valen e and ondu tion bands. The bulk self-energy orre tions amount to 0.1 eV for
o upied and +0.6 eV for uno upied states. In ontrast, the self-energy shift of the As lone
pair equals about +0.1 eV and that of the uno upied surfa e state is intermediate between
the bulk Ge o upied and uno upied shifts and equals +0.45 eV [428, 432.
Quasiparti le orre tions often improve the dispersion of o upied and uno upied LDA
surfa e states and agree well with experiment. Self-energy orre tions an either in rease or
73

onsistent improvement over LDA of al ulated valen e band o sets ompared to experiment
an be a hieved [413.
Further appli ations. An overview over valen e band o set al ulations in the GWA
and expli it al ulations for the Inx X1 x As-Iny Y1 y Z (X = Ga, Al; Y = Ga, Al; Z = P,
As) system is given in Ref. [413. These alloy al ulations are based on the virtual rystal
approximation, whi h may not apture lo al bond-length u tuations in the real alloy that
ould systemati ally hange the interfa e dipole.
. S hottky barriers
At a metal/insulator interfa e su h as Al/GaAs(110), alignment of the metal and semi ondu tor Fermi levels leads to the reation of a 100-1000 
A thi k spa e harge layer on the
semi ondu tor side whi h, via Poisson's equation, bends the valen e and ondu tion bands.
Ele trons (holes) that ow from the metal into the n-type (p-type) semi ondu tor must
over ome the so- alled S hottky barrier if the metal Fermi level is pinned inside the semi ondu ting gap Eg (for a re ent review of S hottky barriers see Ref. [424). The n-type and
p-type S hottky barriers Bn and Bp are de ned in terms of the ondu tion band minimum
E and the valen e band maximum Ev of the bulk semi ondu tor and the bulk metal Fermi
energy EF as
)
Bn = E EF
) Bp + Bn = Eg :
(128)
Bp = EF Ev
In analogy with Eq. (127) and negle ting density rearrangements beyond LDA, we obtain
with  as the quasiparti le orre tion to E EF and Ev EF , respe tively,

Bn(p) = BnLDA
(p) + 

(129)

where BnLDA
(p) is the LDA S hottky barrier.
In ontrast to the LDA S hottky barriers, the bulk quasiparti le orre tions do not depend
upon the atomi stru ture of the interfa e and equal 0.22 eV in the ase of Al/GaAs(110) [425,
426, 427. This orre tion amounts to 20-60% of the LDA barrier depending on the parti ular
interfa e stru ture hosen and establishes the importan e of many-body orre tions.
Self-energy e e ts lead not only to orre tions to the S hottky barrier height but also
to semi ondu tor band-gap narrowing in the 1-10 
A vi inity of the metal-semi ondu tor
interfa e [425, 426. Classi ally, an ele tron in the semi ondu tor experien es an additional
energy-lowering, ele trostati potential whose e e t an be des ribed by the intera tion of
the ele tron with its image harge in the metal. With " as the diele tri onstant of the
semi ondu tor and z as the ele trons distan e from the interfa e, the energy lowering of the
ondu tion band equals 1=(4"z ). Analogously, the valen e band is bent upwards by the same
amount. Quasiparti le al ulations for Al/GaAs(110) give a signi ant band gap redu tion
of 0.4 eV ompared to a bulk GWA gap value of 1.1 eV ( ore-polarization e e ts are omitted, see Refs. [425, 426) and suggest that the narrowing of the gap is mainly due to the
bending of the ondu tion band rather than being equally distributed between the valen e
72

valen e band o set is then given as


Ev = Ev;A

LDA
Ev;B + Vdipole = Ev;A

LDA +  + V
Ev;B
dipole :

(127)

Under the assumption that LDA des ribes the interfa e dipole orre tly, i.e., Vdipole =
related to absolute energy shifts in GWA [416,
LDA E LDA and the
al ulation, whi h gives Ev;A
v;B
interfa e dipole, and from bulk GWA al ulations, whi h determine . This implies that
interfa e GWA al ulations are omputationally less demanding than quasiparti le al ulations of superlatti es sin e they require the onsideration of only the bulk rather than the
generally mu h larger superlatti e unit ell. Negle t of the di eren e between the real and
the LDA interfa e dipole potential is onsidered to be a good approximation, sin e LDA
des ribes semi ondu tor densities to within a few per ent.
Density distributions at semi ondu tor interfa es su h as GaAs-AlAs are smooth due
to the similar average valen e ele tron densities and s reening properties of the onstituent
materials (average valen e ele tron density = 0.177 ele trons/
A3 (GaAs), 0.176 ele trons/
A3
(AlAs); diele tri onstant = 10.8 (GaAs), 8.2 (AlAs)). More inhomogeneous systems su h
as metal-va um interfa es require a self- onsistent treatment of quasiparti le wave fun tions
as dis ussed in Se tion 28.
Quasiparti le orre tions to the valen e band o set at a GaAs-AlAs interfa e [410, 417
amount to about 0.1 eV or 30% of the valen e band o set of 0.41 eV determined in LDA.
Self-energy orre tions are ru ial to obtain a theoreti al valen e band o set of 0.530.05
eV in good agreement with experimental values of 0.53-0.56 eV [418, 419.
As in the ase of GaAs-AlAs, Table 28 shows that quasiparti le e e ts in rease the
valen e band o set at a zin blende GaN-AlN (110) nonpolar interfa e by about 30% or
0.25 eV [196. The size of the self-energy orre tion for the non-polar interfa e as well as the
large dis repan y between experimental valen e band o sets for the polar wurtzite GaN-AlN
(0001) interfa e (0.700.24 eV [422 vs. 1.360.07 eV [423 in omparison to a theoreti al
value of 1.18 eV) suggests that self-energy orre tions are important in understanding GaNAlN interfa es. Treatment of the Ga 3d ele trons as valen e rather than ore ele trons
in reases the LDA valen e band o set by about 50% and swit hes the sign of the LDA
interfa e dipole [196. For pra ti al purposes, one an treat the Ga 3d ele trons via nonlinear
ore orre tions [205 in the GWA, i.e., rely upon error an ellation between the negle t of
wave fun tion relaxation and the negle t of s reening and ex hange (see Se tion 15 a for a
dis ussion of the GWA treatment of d ele trons). This approa h gives good quasiparti le
energies in omparison with experiment even for II-VI semi ondu tors [51.
Quantitatively a urate predi tions of transport properties require an a ura y of quasiparti le al ulations that is better than the relevant energy s ale of about 25 meV set by room
temperature. As dis ussed in Se tion 18 a, only few independent quasiparti le al ulations
agree to within 50 meV for quasiparti le energies or even quasiparti le energy orre tions.
Di eren es on the order of a few tenths of an eV between quasiparti le al ulations and
also between theory and experiment are the norm, indi ating that the determination of selfenergy orre tions to band o sets pushes the a ura y limits of the GWA. Nevertheless, a

LDA , and ignoring possible ompli ations


Vdipole
Ev is determined from an LDA super ell

71

in photo urrent experiments [407. Dire t, zone-folded transitions are predi ted at 1.24,
1.34, 1.76, and 1.86 eV and explain features observed in ele tro-re e tan e measurements
at 1.1-1.25 and 1.8 eV [407. For a Ge substrate, Si4 Ge4 is predi ted to be approximately a
dire t-gap semi ondu tor.
Con nement of states in either the Si or the Ge region of the superlatti e should not have
a signi ant quantitative e e t on the expe tation value of the self-energy operator sin e the
self-energy e e ts in Si and Ge are very similar as shown in Se tion 18. Fig. 33 shows the
qualitative agreement between quasiparti le shifts for bulk Si, tetragonally strained Ge, and
Si4 Ge4 on a sili on substrate. This agreement o urs after all quasiparti le energies have
been aligned at the top of the valen e band.
Further appli ations. Band-gap variation and variation of dire t-indire t band-gap transitions due to a hange of superlatti e period or of on entration in the ase of ordered alloys
have been studied in GaN/AlN [408, GaAs1 x Nx , and AlAs1 x Nx systems [49. At the interfa e of (GaAs)n (AlAs)n (001) (n=1,2) superlatti es [409, 410, 411, ele trons in ex ited
states whose density is lo ated on ation sites a umulate in the GaAs- rather than the
AlAs-region of the superlatti e, due to the relative repulsive hara ter of the Al versus the
Ga pseudopotential. This lo al bonding e e t auses the GWA dire t gap in 11 and 22
superlatti es to be lower in energy than the pseudodire t gap in ontrast to e e tive-mass
model al ulations. E e tive mass al ulations (i) miss the lo al bonding e e t, and onsequently (ii) show an inverted ordering of bands [411.
b. Interfa es
An interfa e between two dissimilar semi-in nite semi ondu tors A and B is hara terized
by the di eren e in the valen e band energy between the two bulk regions, the valen e band
o set Ev , and the orresponding ondu tion band o set E [413 as shown in Fig. 34.
Interfa es play an essential role in heterojun tion devi es, and the band o sets Ev and E
determine their transport properties [414. The qualitative e e ts of interfa e orientation,
defe ts, polarity, and strain on band o sets an be studied using density fun tional theory.
However, a more a urate predi tion of valen e and ondu tion band o sets requires a quasiparti le approa h [413. Sin e the sum of the valen e and ondu tion band o sets equals the
known band gap dis ontinuity between the semi ondu tors A and B, Egap = Ev + E ,
self-energy orre tions of only the valen e-band o set are dis ussed in this subse tion.
Within a few monolayers of the sharp interfa e harge density rearrangement leads to the
formation of an interfa e dipole whi h auses a potential step between the bulk materials
[413. The dipole ontribution an be ombined with the bulk-derived valen e band edge
positions to obtain a band o set for a parti ular interfa e. Let the volume-averaged [415,
ele trostati (Hartree) potential hVH iA(B) de ne an absolute energy level with respe t to
whi h the quasiparti le valen e band edges Ev;A(B) are measured. The (LDA) dipole potential
(LDA) = hV i(LDA) hV i(LDA) . Denote the di eren e in the quasiparti le
is given as Vdipole
H A
H B
orre tions to the bulk LDA band stru ture of the semi ondu tors A and B as . The
70

3.5-3.7 eV [397, 398, 399 and is reprodu ed reasonably well by a quasiparti le value of
3.0 eV whi h orre ts an LDA result of 1.6-1.7 eV. Quasiparti le al ulations for perfe tly
ordered, rystalline C60 lead to an about 30% in rease in the LDA band width as shown
in Fig. 32 resulting in GWA band widths of 0.9 eV, 0.7 eV, and 0.8 eV for Hu , T1u , and
T1g , respe tively. Sin e LDA overestimates the experimental band width, further physi s is
needed to explain the experimental band-width narrowing within a quasiparti le framework.
Four auses for a la k of dispersion in angle-resolved photoemission spe tra of the H1u ,
T1u , and T1g bands [338, 394 are (i) the multiband nature of the system, (ii) orientational
disorder, (iii) integration over re ipro al latti e ve tors perpendi ular to the sample surfa e,
and (iv ) nite experimental resolution. Cal ulations [338, 394 of the photoemission spe tra
that are based on a Slater-Koster parametrization of the quasiparti le energies and that
in lude orientational disorder of the C60 mole ules agree with experiment. These al ulations
prove that a la k of dispersion of the Hu , T1u , and T1g band omplexes of disordered mole ular
C60 solid in experiment annot be interpreted as a sign of strong ele tron-ele tron orrelations
[338, 394.
Further appli ations. Band-width renormalization in A3 C60 (A = K, Rb) due to the T1u
plasmon has been examined by Gunnarsson within the framework of the GWA [400. Quasiparti le al ulations on periodi ally repeated BN sheets with interlayer distan es varying
from 5.5 
A to 13.5 
A an be used to dedu e the band stru ture of BN nanotubes via zone
folding as shown by Blase et al. [401, 402. The layered stru tures have a al ulated indire t
band gap of about 5.5 eV between the top of the valen e band at K and the bottom of the
ondu tion band at whi h is relatively independent of the interlayer distan e.
20. SUPERLATTICES { INTERFACES { SCHOTTKY BARRIERS
a. Superlatti es
Simple superlatti es onsist of periodi ally repeated units of n layers of a material A sta ked
onto m layers of a material B and are designated by An Bm . The superstru ture of these
arti ial ompound semi ondu tors gives rise to a variety of new physi al phenomena su h
as on nement, built-in strain, Brillouin zone folding, and two-dimensional ele tron gas
behavior [403, 404, 405. Variation of superlatti e hara teristi s permits fabri ation of
semi ondu tor devi es with ustom-tailored ele troni properties. Mole ular beam epitaxy
(MBE) allows the growth of superlatti es with monolayer pre ision [404. Quasiparti le
al ulations for superlatti es An Bm are identi al to bulk al ulations with the sole ex eption
that the unit ell ontains n layers of material A and m layers of material B and is therefore
a fa tor (n + m)=2 larger than the unit ell of the orresponding binary semi ondu tor AB.
The rst appli ation of GWA for a semi ondu tor superlatti e was for Si4Ge4 [406, 407,
a superlatti e based on the indire t-gap semi ondu tors Si and Ge, sin e this stru ture
(i) ould be a pseudo-dire t-gap material suitable for optoele troni appli ations, and (ii)
is ompatible with Si-based hip te hnology. However, for Si substrates GWA nds two
indire t band edges at 0.85 and 0.95 eV in omparison to values of 0.78 and 0.90 eV obtained
69

Gunnarsson [55 report an LMTO study of NiO, and Massidda et al. [91, 54, 380 use a
model-GWA approa h [381 to determine the band stru ture of MnO, NiO, and CaCuO2 .
The large dis repan y between the LSDA and the experimental gap, for instan e, in the ase
of NiO suggests that the initial LSDA system and in parti ular the LSDA wave fun tions
are not good approximations to the quasiparti le system and wave fun tions. This suspi ion
is on rmed in a tual al ulations [54, 55. Self- onsisten y is generally used to onstru t
a better basis set than the LSDA basis set. Aryasetiawan and Gunnarsson [55 use an approximate self- onsisten y s heme implemented via a modi ation of the LSDA one-parti le
Hamiltonian, whereas Massidda et al. [54 expand the quasiparti le wave fun tions in a basis
of o upied and uno upied LSDA wave fun tions and determine the expansion oe ients
self- onsistently.
The basi physi s behind the model-GWA al ulation of Massidda et al. is the separation
of the s reened intera tion W into a short-range part W IEG that des ribes the s reening of
an inhomogeneous ele tron gas and a long-range part W that a ounts for the in omplete
s reening in insulators [381. The short-ranged ontribution W IEG is approximated by the
lo al, energy-independent Kohn-Sham ex hange- orrelation potential [39. The long-ranged
s reened intera tion W must de ay as 1=jr r0j for large jr r0 j and a ounts for the in rease
of, for example, the NiO LSDA gap of 0.3 eV by 3.40.4 eV [54.
Table 27 summarizes GWA results for transition-metal oxides and shows that (i) fundamental energy gaps are in fair agreement with experiment, and (ii) magneti moments
are in good agreement with experiment. Both quantities show signi ant improvement over
LSDA and are of omparable or better a ura y than LDA+U or self-intera tion- orre ted
al ulations. The inability of RPA-based GWA to reprodu e the satellites in photoemission
spe tra is attributed to the la k of short-range orrelations in GWA and is reminis ent of
the failure to reprodu e the 6 eV satellite in Ni (see Se tions 5 and 26 and Ref. [68).
While self- onsisten y in GWA al ulations in reases the oxygen 2p hara ter of the highest
valen e band [54 that in rease is not enough to eliminate the dominan e of the Ni 3d state
and to a hieve agreement with experiment [55.
. C60 and related systems
Quasiparti le al ulations des ribe the ele troni stru ture of solid C60 well (see Ref. [394 for
an overview of experimental and theoreti al results for the C60 band stru ture). Estimates
of on-mole ule and nearest-neighbor-mole ule Hubbard-U parameters of 1.0 and 0.5 eV,
respe tively, are of the same order as the measured band width of about 0.5 eV of the highest
o upied (H1u ) and two lowest uno upied (T1u and T1g ) multiband omplexes. Inspite of
these intermediate to strong ele troni orrelations, GWA al ulations for fa e- entered ubi
C60 des ribe the fundamental energy gaps quantitatively well [338, 394, 395. Self-energy
orre tions double the LDA fundamental gap of 1.04 eV to a quasiparti le gap of 2.15 eV that
ompares well with a gap of 1.850.1 eV obtained in mi rowave ondu tivity experiments
[396 or of 2.3-2.7 eV dedu ed from dire t and indire t photoemission experiments [397,
398, 399. The Hu -T1u peak-to-peak distan e in the experimental density of states equals
68

arriers, and (ii) a hange in the pole stru ture of the Green fun tion in the doped ase.
In rst-order perturbation theory and negle ting the unimportant Hartree ontribution the
quasiparti le band-gap hange equals
Enk =

nk (r)(r; r0 ; "nk)nk (r0 )drdr0; Egap = ECBM

EV BM

(125)

where ( denotes onvolution in frequen y spa e)


(r; r0 ; E ) = Gdoped  W doped Gintrinsi  W intrinsi = Gdoped  W +G  W intrinsi : (126)
The rst term des ribes the hange in the s reening of the ele tron-ele tron intera tion and
turns out to be the dominant ontribution to band-gap narrowing, equaling about 0.1 eV at
a arrier on entration of n = 1020 m 3 and about 0.25 eV at n = 1021 m 3 . The e e t of
s reening be omes stronger with in reasing arrier on entrations. The se ond term stems
from the hanged pole stru ture of the Green fun tion and also in reases with in reasing
on entration. However, its absolute ontribution to the band-gap narrowing is negligible
and amounts to less than 10 meV for on entrations smaller than 1022 m 3 .
First-prin iples GWA al ulations identify the negle t of frequen y dependen e of the
intrinsi diele tri matrix as an unphysi al assumption ommon to many model al ulations
of arrier-indu ed band-gap narrowing [375. The frequen y dependen e of the intrinsi
diele tri matrix in reases band-gap narrowing by about 30% of the dominant Gdoped W
ontribution at n = 1020 m 3 and by about a fa tor of two at n = 1021 m 3 , and should not
be negle ted. Other e e ts su h as lo al elds in the intrinsi diele tri matrix or the des ription of the ondu tion band states either as LDA states or as plane waves are unimportant
sin e the main ontributions to the modi ation of s reening arise from the long-wavelength
omponent.
b. Transition-metal oxides
The large dis repan y between lo al spin density (LSDA) fun tional al ulations and experiment indi ates that strongly orrelated transition-metal oxides pose a hallenge to perturbation theory al ulations su h as the GWA. Transition-metal oxides su h as NiO are
antiferromagneti insulators whose 3d onsite repulsion is about 8 eV and hen e on the same
s ale as the 3d band width whi h is indi ative of strong orrelations between the 3d ele trons.
The band gap in NiO is a harge transfer gap, i.e., if a hole with a small binding energy is
reated on the Ni site it is lled with a high probability by an oxygen 2p ele tron. Experimentally, the hole in the highest valen e band has a strong oxygen 2p hara ter in ontrast
to lo al spin density al ulations that show a predominant Ni 3d hara ter. In addition, the
LSDA severely underestimates the band gap and magneti moment in transition-metal oxLSDA = 0:2 eV vs. E exp = 4:0 eV; LSDA  1 vs. exp = 1:7 1:9 )
ides su h as NiO (Egap
B
B
gap
sin e LSDA is unable to properly des ribe lo alized states in these materials.
A urate treatment of the transition-metal d and oxygen 2p states is di ult and has
limited the number of transition-metal-oxide quasiparti le al ulations. Aryasetiawan and
67

IV. Semi ondu tors and insulators


This hapter gives a omprehensive overview over appli ations of quasiparti le al ulations
to semi ondu tors and insulators. These appli ations are grouped a ording to bulk materials, superlatti es and interfa es, surfa es, defe ts, pressure dependen e and ex itons. The
last se tion dis usses quasiparti le al ulations for atoms and mole ules.
19. BULK
The te hni al details of GWA al ulations in bulk semi ondu tors and insulators and results
for ve prototypi al semi ondu tors are extensively dis ussed in Chapter III. Figure 3 shows
an overview over { to the best of our knowledge { all GWA al ulations for semi ondu tors
and insulators published so far. This se tion is therefore limited to three examples of the
relevan e of GWA to des ribe the ele troni stru ture of materials: (i) band-gap narrowing
in n-type Si, (ii) transition-metal oxides, and (iii) solid C60 and related systems.
a. Band-gap narrowing in Si
Two ompeting pro esses in uen e the band-gap modi ation of Si upon n-type doping [373:
(i) Ele trons ll ondu tion bands up to some new Fermi level and e e tively in rease the
photoex itation gap of valen e ele trons. (ii) The ondu tion ele trons form a low-density,
\metalli " gas of arriers and in rease s reening of the ele tron-ele tron intera tion whi h
redu es the band gap. A quantitative understanding of these e e ts on the band gap of doped
semi ondu tors is important sin e it a e ts the performan e of semi ondu tor devi es.
Quasiparti le al ulations [374, 375 have so far onsidered band-gap narrowing in doped
Si and nd (i) LDA is inadequate for the des ription of band-gap narrowing, (ii) the modi ation of s reening due to ex ess arriers dominates band-gap narrowing in the GWA
al ulation, and (iii) the energy dependen e of the intrinsi diele tri matrix { omitted in
all model al ulations (for a review of model al ulations see Ref. [375) { modi es band-gap
narrowing by up to a fa tor of two for ommon dopant on entrations in Si. A dire t omparison of GWA al ulations [374, 375 with experiment [376, 377, 378 is inappropriate sin e
the self-energy al ulations do not onsider ele tron-donor s attering [379. With VH and
Vx as hanges in the ele trostati and LDA ex hange- orrelation potentials upon introdu tion of additional ele trons in the system, the LDA ontribution to band-gap narrowing
an be al ulated in rst-order perturbation theory as
"nk =

nk (r) [VH (r) + Vx (r) nk (r)dr

(124)

whi h even for as high ele tron on entrations as n = 4  1020 m 3 a e ts the band gap by
less than 5 meV [375.
In a GWA al ulation ontributions to band-gap narrowing result from (i) a hange in
the s reening of the ele tron-ele tron intera tion due to the presen e of additional harge
66

state at X and L redu e to 0.14 eV and 0.04 eV when 60 Gaussian orbitals are used as shown
in Table 15. Also, deviations between pseudopotential results that in lude ore-polarization
and ore-relaxation e e ts [43 and s alar-relativisti , all-ele tron LMTO al ulations [290
are likely to result from the negle t of ombined orre tions in the LMTO wave fun tions
and from the atomi sphere approximation.
. Sili on arbide and gallium nitride
Numeri al and experimental data on the quasiparti le band stru ture of SiC and GaN are
s ar e. To the best of our knowledge only three GWA al ulations for SiC have been published so far: one based on Gaussian orbitals [114 and two based on plane-waves [42, 130.
Table 24 demonstrates that agreement between the three al ulations is unsatisfa tory. In
parti ular, the average deviation in the LDA band stru ture between all three approa hes
is 0.19 eV (maximum 0.41 eV for the L1 -state), the average deviation in the quasiparti le
energies is 0.36 eV (maximum 0.82 eV for the X5 -state), and the average deviation in the
quasiparti le shifts is 0.29 eV (maximum 0.67 eV for the X5 -state). It is urrently not
understood what auses the signi ant di eren es in the LDA and quasiparti le band stru tures of these three independent al ulations [362. All three al ulations, however, give a
good a ount of experimentally a essible interband transitions and energies as shown in
Table 25. Average deviations from experiment ex luding the L1 state range from 0.22 eV
[42 to 0.24 eV (Ref. [114, 0.20 eV if 60 Gaussians are used) to 0.29 eV [130.
All three al ulations pla e the L1 -state between 6.30 and 6.76 eV in marked ontrast to
experiment (4.2 eV). The di eren e between theory and experiment is well beyond theoreti al
and experimental un ertainties. The agreement of the three GWA al ulations for the L1
state strongly suggests that the experimental 4.2 eV transition annot be interpreted as an
indire t transition between quasiparti le-like 15v and L1 states [114.
GaN is a very important material for opti al devi es su h as blue light-emitting diodes and
blue lasers [365. However, two obsta les impede theoreti al progress [189, 366: (i) the Ga 3d
ele trons intera t strongly with the N 2s ele trons, and (ii) GaN band stru tures are sensitive
to the hoi e of the N pseudopotential. In GaN the 3d ele trons in LDA lie at the bottom
of the valen e band and hybridize with the s bands. In LDA, d ele trons are underbound
in omparison to experiment leading to a strong, unphysi al s-d hybridization. A proper
treatment of the Ga 3d ele trons requires a self- onsistent determination of the wave fun tions
and the in lusion of ex hange with the 3s and 3p ele trons as explained in Se tion 15 a.
A omputationally heaper, surprisingly a urate, approa h for the determination of the
quasiparti le band gap is the treatment of the 3d ele trons via nonlinear ore orre tions [205
whi h has been adopted in the plane-wave al ulations of Refs. [42, 47, 367. Variations in the
quasiparti le energies of the lowest-lying ondu tion band for the three di erent al ulations
amount to about 0.2 to 0.7 eV and are signi antly larger than the generally quoted GWA
un ertainty of 0.1 eV. In part, these variations may result from (i) the hoi e of di erent
pseudopotentials as spe i ed in Table 26, and (ii) the use of a model diele tri matrix in
Ref. [47 ompared to RPA diele tri matri es in Refs. [42 and [367.
65

small GWA orre tions to the highest o upied LDA energy. Indeed, GWA al ulations
[6, 44 that are based on an LDA al ulation using RPA orrelation [356 or GW al ulations that are onsistent with Ceperley-Alder ex hange- orrelation [102 shift the highest
o upied state of Si by only 0.1 to 0.2 eV and may be the most appropriate, for example,
for the determination of valen e band o sets [357. Note that the self-energy orre tions to
the highest o upied LDA state in rease with an in reasing energy gap and ioni ity of the
material and ex eed, for example, a negative orre tion of 1 eV in the ase of LiCl even with
the use of RPA orrelation [44.
Figure 31 ompares the results of an LDA and GWA al ulation [42 with photoemission
and inverse photoemission experiments. The size of a typi al experimental resolution is 0.27
eV in energy and 0.1 
A 1 in momentum [342. In numeri al al ulations the momentum is
well de ned, while the energy un ertainty is estimated to be about  0.1 to 0.2 eV from
the above dis ussions. The agreement between theory and experiment is good along the L
dire tion. The lowest ondu tion band shows the largest dis repan y between theory and
experiment and seems to lie slightly higher than the al ulation. Along the X dire tion
agreement between experiment and theory is satisfa tory. In part due to the large experimental momentum un ertainty, theory and experiment still agree to within the respe tive
un ertainties. However, the lowest valen e band as well as the rst two ondu tion bands {
the 1 and the 02 bands { show less dispersion than the theoreti al predi tion.
b. Germanium and gallium arsenide
Ge and GaAs are more di ult theoreti ally due to the importan e of the extended ore
and relativisti e e ts. The ore an in uen e the valen e energies in several ways: (i) ore
relaxation, (ii) ore-valen e ex hange, (iii) ore-valen e orrelation, (iv ) ore polarization.
As shown in Se tion 12, an improved treatment of ex hange and orrelation e e ts due
to ore ele trons beyond LDA in reases the dire t band gaps of Ge and GaAs obtained
in standard GWA al ulations by 0.32 eV and 0.40 eV, respe tively, and leads to good
agreement with experiment (Ge (GaAs): 0.85 (1.42) eV from theory vs. 0.89 (1.52) eV from
experiment [43). As shown in Table 22, s alar-relativisti GWA al ulations for Ge that
treat ore-valen e ex hange and orrelation on an LDA level (i) deviate signi antly from
experiment (e.g., dire t gap of 0.48 eV [42 in ontrast to 0.89 eV in experiment), and (ii)
agree to within 0.1-0.3 eV with ea h other if an update of quasiparti le energies [44 and
insu ient onvergen e (Ref. [114, see Se tion 15 a) are a ounted for. An update of the
0 gap signi antly
energy spe trum of the Green fun tion is bound to a e t the 025v
2
be ause the se ond iteration deals with a semi ondu tor rather than a semimetal.
The results for GaAs are summarized in Table 23. Due to the negle t of ore-valen e
intera tions the experimental band gap at is underestimated by about 0.4 eV in standard
GWA al ulations [353. The quasiparti le energies vary by 0.3 to 1.5 eV between the di erent al ulations due to di erent approximations as detailed in the aption of Table 23 and
dis ussed in Se tions 15 a, 16, and 18 a. In parti ular, deviations of 0.65 eV and 0.3 eV with
the 40 Gaussian orbital al ulation of Rohl ng et al. [114 for the lowest ondu tion band
64

(ii) The a ura y of onverged plane wave al ulations for the same transitions as above
is 50 meV in LDA and 50 meV in GWA and omparable to hemi al a ura y.
(iii) Plasmon-pole approximations do not a e t the lowest dire t band gaps in Si by more
than 50 meV.
(iv ) GWA improves signi antly upon the LDA des ription of ex ited states and gives
agreement with experiment within the experimental and omputational un ertainties.
The on lusions (i), (ii), and (iv ) are state- and material-dependent. Take the 02 state in
Si, whi h is parti ularly di ult to onverge, as an example. Here, the deviations between
all al ulations are 0.39 eV in LDA and 0.41 eV in GWA. The deviations for well- onverged
plane-wave al ulations are 0.1 eV in both LDA and GWA, well outside hemi al a ura y. In
addition, materials that are less \benign" than Si, i.e., in whi h, for example, ore ele trons
or relativisti e e ts are relevant, exhibit larger variations in LDA and GWA energies as will
be shown below. Ex eptions to (iv ) will be dis ussed in Chapters IV and V.
The plasmon-pole approximation is expe ted to break down for quasiparti le energies of
the order of the Si plasmon energy, !pl = 16:7 eV (see Table 3). Comparing plane wave
al ulations, with the ex eption of Ref. [6, for the lowest valen e band energies at , X , and
L shows that the plasmon-pole approximation leads to an arti ial widening of the valen e
band width. The widening amounts to about 0.25 eV and shows very little variation ( 20
meV) between , X , and L. Taking the full frequen y dependen e into a ount improves
agreement with experiment at the L point but leads to disagreement with experiment at the
point if the experimental value of 12.5 eV is used, as shown in Table 21. The a ura y
of the ommonly quoted experimental value of 12.50.6 eV has been questioned [89, 302.
Re ent experiments nd a valen e band width at of 11.4 eV [351 and 11.2 eV [352 in
good agreement with the al ulations by Fleszar and Hanke [102 and Rieger et al. [103.
Fleszar and Hanke [102 ompare standard GWA al ulations for Si with GW al ulations (see, e.g., Se tion 14) that in lude LDA vertex orre tions in the diele tri matrix and
the self-energy. In lusion of vertex orre tions (see also Se tion 14, Eqs. (97) and (98)) (i)
shifts absolute energies by about 0.5 eV, (ii) a e ts relative energies of valen e and ondu tion bands lose to the Fermi level by less than 50 meV, and (iii) leads to larger shifts of up
to 0.15 eV for the relative energies of low-lying valen e states.
Absolute energies depend on the hoi e of the ex hange- orrelation potential [44, the
degree of onvergen e [102, and the hoi e of the self-energy approximation (GWA vs.
GW , Ref. [89, 102) as dis ussed in Se tion 14. As a result, absolute energies u tuate
from +0.07 eV [6 to 0.65 eV [42 for the 025v state. Absolute energies agree to within 0.16
eV ( 0.49 eV to 0.65 eV) for well- onverged, plane-wave-based GWA al ulations whose
LDA ex hange- orrelation is based on the Ceperly-Alder data for the homogeneous ele tron
gas [355. For these al ulations, the main self-energy orre tion is in the valen e and not in
the ondu tion band [102.
In density fun tional theory the highest o upied valen e energy is given exa tly [39, 40,
and, under the assumption that LDA is a good approximation to DFT, one would expe t
63

18. GWA CALCULATIONS FOR FIVE PROTOTYPICAL SEMICONDUCTORS


This se tion summarizes all published [336 quasiparti le al ulations for ve prototypi al
semi ondu tors and is intended to serve as a referen e for readers with a detailed interest
in the subje t. In addition, the a ura y of quasiparti le al ulations is assessed by omparison of independent al ulations for several materials and is shown to be (i) state- and
material-dependent, and (ii) often signi antly larger than the ommonly quoted 0.1 eV.
All quasiparti le al ulations yield good results for Si, suggesting that tests of quasiparti le
approa hes annot be limited to this material [337.
Relativisti e e ts and the treatment of ore ele trons have signi ant e e ts on LDA
band gaps as demonstrated in Table 33. These e e ts have to be onsidered in standard
GWA al ulations to a hieve good agreement with experiment as demonstrated by the work
of Shirley et al. [43, 338.
a. Sili on
Sili on is a prototypi al semi ondu tor that has been studied in seven independent GWA
al ulations based on (i) pseudopotentials and plane waves [5, 6, 42, 102, 103, (ii) pseudopotentials and Gaussian orbitals [114, and (iii) LAPW [285. In ontrast to all other al ulations, the pseudopotential al ulations of Rieger et al. [103 and of Fleszar and Hanke [102
avoid the plasmon-pole approximation by expli itly omputing the frequen y-dependent intera tion.
Comparison of both the LDA and GWA energy variations between the di erent al ulations for the lowest ondu tion band states of Si listed in Table 21 reveals
(i) all GWA al ulations for the lowest ondu tion band lie within 0.2 eV of the range of
experimental energies observed,
(ii) between all al ulations, the variations in both LDA and GWA energies of the lowest
ondu tion band are 0.03 eV and 0.14 eV at , 0.05 eV and 0.30 eV at X , and 0.1 eV
and 0.17 eV at L, respe tively,
(iii) omparison of plane wave al ulations without an update of the Green fun tion and
disregarding [354 Ref. [6 gives variations for the lowest ondu tion band energy of 30
meV and 40 meV at , 50 meV and 40 meV at X , and 50 meV and 50 meV at L, for
LDA and GWA, respe tively,
(iv ) an update of the energies in the Green fun tion (see Se tion 13) in reases the fundamental gap by about 0.1 eV.
Four main on lusions an be drawn from the above observations:
(i) LDA and GWA al ulations for the lowest dire t band gaps in the prototypi al semi ondu tor Si are a urate to within 0.1 eV for LDA and 0.1 to 0.3 eV for GWA.
62

Instead, a \blo k- olumn" gather operation using the MPI GATHER fun tion is performed
whi h is illustrated in Fig. 30. The basi idea is to assemble all r-ve tors and a blo k of G0 ve tors on one PE su h that a lo al 3D FFT on P 0 (k; r; G0; i ) an be done after reordering
the r-ve tors in FFT order.
Although the Green fun tion is onstru ted with lose to perfe t load balan ing by parallelizing over the r-ve tors in the irredu ible real-spa e unit ell, the load balan ing for the
onstru tion of the independent-parti le polarizability in re ipro al spa e is less favorable
sin e now the symmetry of the r-ve tors in the irredu ible real-spa e unit ell is important
as well. However, larger systems have many r-ve tors in the irredu ible real-spa e unit ell
and low symmetry and di eren es in symmetries should average out.
After all these steps, one obtains P 0(k; G; G0 ; i ) for all G-ve tors and a blo k of G0 ve tors whi h is written to disk via PE0 for all k-points and all times i . The next step is the
Fourier transform with respe t to imaginary time. To do this Fourier transform, PE0 reads
quadrati submatri es in (G; G0 ) of P 0 (k; G; G0 ; i ) for all times i and distributes these
submatri es over a quadrati grid of pro essors. The time Fourier transform is done lo ally.
Further matrix operations su h as the onstru tion of the RPA diele tri matrix and of the
s reened intera tion are done using S aLapa k routines for the multipli ation and inversion
of distributed matri es.

61

polarizability (Eq. (112)) in real spa e and imaginary time and the subsequent transformation
of the independent-parti le polarizability to re ipro al spa e and imaginary frequen y [312.
All subsequent operations in the ode are either the exa t inversion (for instan e one-to-all
broad ast and single-node a umulation) or slight modi ations of these basi operations. It
is su ient to dis uss parallelism only up to the onstru tion of the s reened intera tion in
re ipro al spa e and imaginary frequen y whi h is shown s hemati ally in Figs. 29 and 30.
Using managed I/O, PE0 starts by reading input information about the latti e, k-points,
LDA energies, et . and by broad asting it to all other PEs. Then in a small serial portion
of the program PE0 reads the Fourier oe ients for ea h band and FFTs them to obtain
the periodi parts of the Blo h wave fun tions unk(r) and unk(r0 ). These wave fun tions are
written to dire t a ess les. For unk (r) the re ord index is the FFT index of the r-ve tor
in the real spa e unit ell. The re ord ontains unk(r) for all bands and all k-points. For
unk (r0 ) the re ord index is the number of the spe ial k-point and the re ord ontains all
r0 -points in the real spa e unit ell for all bands.
Next an external loop over imaginary time starts in whi h the non-intera ting propagator
at imaginary times i and for all r-ve tors in the irredu ible real-spa e unit ell is determined. Ea h PE has a list of r-ve tors for whi h it al ulates G0 (r; r0; i ) for a parti ular
time i and all r0 in the intera tion ell a ording to Eq. (111). For example, if the number
nviu of r-points in the irredu ible real-spa e unit ell is 55 and the number of pro essors
is 4, then PE0 al ulates G0 for the rst 13 r-ve tors, PE1 for the following 14, and so on.
To al ulate G0 at a point ri , ea h PE needs unk(ri ) for all bands and all k-points as well
as unk(r0 ) for all r0 , all bands, and all k-points. Let rank denote the number of a PE. For ea h
i and ea h node PE0 reads the orresponding wave fun tion information unk(ri ) in real spa e
and sends it to PE rank. At the end PE0 reads the information that it needs for its own
al ulations. Subsequently in a loop over k-points, PE0 reads unk (r0 ) for a parti ular k-point
and broad asts this wave fun tion for all bands and all r0 in the real spa e unit ell to all PEs
as shown in Fig. 29. After ea h PE has nished the loop over k-points and has al ulated
its non-intera ting propagator at i it sends the produ t G0 (ri ; r0 ; +i )G0 (ri ; r0; i ) { i.e.
the independent-parti le polarizability up to a onstant fa tor { to PE0 and PE0 writes the
result to disk. This ommuni ation is the inverse operation of the distribution of unk(ri )
des ribed above. A graphi al des ription of this ommuni ation step is given in Fig. 29.
In the next step PE0 reads the independent-parti le polarizability for di erent ve tors ri
in the irredu ible real-spa e unit ell and distributes P 0(ri ; r0 ; i ) over the di erent pro essors
in an analogous way as is done for the distribution of unk(ri ). Within an external loop over
spe ial k-points ea h PE performs the rst 3D FFT over r0 on node turning P 0 (ri ; r0 ; i )
into P 0 (k; ri ; G0 ; i ).
Two points are important for the 3D FFT: (i) Only those G0 -ve tors in P 0 (k; ri ; G0 ; i )
with jG0 j  Gmax are kept. In the ase of Si, Gmax = 3:4 Hartree whi h orresponds to
169 G0 -ve tors. (ii) After the rst 3D FFT ea h PE ontains all G0 -ve tors and its hunk
of r-ve tors in the irredu ible real-spa e unit ell as well as their images under symmetry
operations of the spa e group of the rystal. Sin e the distribution of the r-ve tors is not
ontiguous in any oordinate, parallel FFTs to perform the next 3D FFT annot be used.
60

(iii) Load balan e. The load balan e is ex ellent. Not ounting the I/O overhead, all
PEs have exa tly the same work load if mod(N b; npes) = 0. If mod(N b, npes) 6= 0, then
the last npes - 1 PEs al ulate the matrix elements MGv for N b =npes ondu tion bands,
while PE0 al ulates MGv for the remaining ondu tion bands. This distribution of work
0 (q; 0) at
load ompensates partially for the extra work that PE0 has to do to assemble PGG
the end of the al ulation ( ompare Fig. 28).
(iv) Communi ation and portability. The algorithm is oarse grain parallel and portable.
PE0 reads and sends the input information and wave fun tion data to all other pro essors.
These al ulate the matrix elements for every k-point and send the results of their al ulation
ba k to PE0. PE0 then assembles the total polarizability. Therefore, for a xed k-point,
ommuni ation o urs only at the beginning and at the end of the omputation. The use
of either MPI or PVM ommuni ation primitives in the oarse-grain parallel ode ensures
portability to di erent platforms [332. The use of symmetry as des ribed in Eq. (116) does
not require any inter-pro essor ommuni ation sin e the matrix elements for all G-ve tors
and hen e for their images under symmetry operations of the little group of q are reated
and used lo ally on ea h pro essor.
(v) Obje t orientation { Use of C++. The entral obje t in the ode is wavefun tion.
As des ribed above, this lass omprises the k-point, at whi h the wave fun tion is de ned,
the number of bands and plane waves kept, the wave fun tion oe ients and energies.
Sending a wave fun tion wvfn tn from pro essor my pe to pro essor your pe only requires
the following statements:
wvfn tn.send(my pe, your pe); and wvfn tn.re eive(my pe,your pe);.
The a tual sending of the data and the ommuni ation primitive used in this pro ess are
hidden from the user. This feature makes a hange from PVM to, e.g., MPI easy, sin e the
hange is done in only one fun tion. Swit hing between PVM and MPI an onveniently be
a hieved via prepro essor dire tives.
During the ourse of the ode development the parallelization s heme hanged twi e.
Parallelization s hemes used are (i) the embarrassingly-parallel approa h of distributing kve tors over PEs [333, (ii) a parallelization over re ipro al G-ve tors [334, and (iii) a
parallelization over ondu tion bands. Changing the ode to a ommodate new parallelization s hemes pro ted immensely from the exibility that an obje t-oriented programming
style o ers ompared to a pro edure-oriented programming style.
0

b. Real-spa e/imaginary-time approa h


For the re ipro al-spa e GWA al ulation, s alability ould be attained by parallelizing over
the ondu tion bands. In real spa e, the r-ve tors in the irredu ible real-spa e unit ell are
an appropriate variable for a s alable parallel implementation [335. The number of ve tors
in the irredu ible real-spa e unit ell is dire tly proportional to system size and hen e the
number of atoms in the system. A system that in reases its size by a fa tor of two an
therefore be handled by using twi e as many pro essors. The important operations in the
program are the assembly of the Green fun tion (Eq. (111)) and of the independent-parti le
59

17. PARALLEL GWA CALCULATIONS


The use of lo al-orbital basis fun tions or re ent, real-spa e algorithms an ut down on the
omputational ost of quasiparti le al ulations as dis ussed in Se tion 15. Another way to
speed up quasiparti le al ulations is the use of massively parallel omputers. This se tion
des ribes parallel algorithms for re ipro al-spa e and real-spa e quasiparti le al ulations.
a. Re ipro al-spa e approa h
The basi idea for a parallel determination of the independent-parti le polarizability (Eq. 116)
and the self-energy (Eqs. (117) and (118)) is to distribute the ondu tion bands over npes
pro essing elements (PEs) during the ourse of the al ulation [42. The prin iple will be
explained for the ase of the independent-parti le polarizability, the ase of the self-energy
an be handled analogously. Let PE0 denote the PE that does all the I/O between the le
system and the parallel ma hine and Nvb= b the number of valen e/ ondu tion bands, NG
the number of G-ve tors, and NP W the number of plane waves.
For ea h k-ve tor PE0 reads the energies and the G-ve tors. Then PE0 reads the rst
N b /npes ondu tion bands (assume mod(N b=npes) = 0 for simpli ity) and sends the information about k-point, energies, G-ve tors, and the rst blo k of ondu tion bands to
PE1. Subsequently, PE0 reads the se ond blo k of ondu tion bands and sends it together
with the k-point, energies, and G-ve tors to PE2, and so on. On e all ondu tion bands are
distributed, PE0 reads the valen e band information for a point k q in the BZq and broad asts that information to all PEs. Then all PEs { in luding PE0 { al ulate the following
expression
(i+1)NXnpes 1 X
o M v (k; q)[M v (k; q)
G
G
:
(123)
"
" ;k
v;
k
q
v
=iN npes
Finally, the results of this al ulation are added up via a single-node a umulation on PE0.
For a graphi al des ription of the algorithm see Fig. 28. The important features of this
parallel implementation are:
(i) Storage requirements. The storage needed for omplex wave fun tions on ea h PE
is proportional to (Nvb + N b =npes)NP W . The memory requirements per node for wave
fun tions in rease approximately linearly with system size sin e Nvb  N b and sin e an
in reasing number of pro essors an ompensate for in reasing system size. For the matrix
elements MGv the storage requirements are proportional to Nvb (N b =npes)NG , whi h leads
to a quadrati memory in rease per node with system size. The use of massively parallel
omputers leads to a gain in memory per node by one order in system size for both wave
fun tions and matrix elements.
(ii) S alability. The in rease of the volume of the system by a fa tor of two leads to twi e
as many ondu tion bands. The orresponding matrix elements an be al ulated e iently
by using twi e as many pro essors leading to a s alable algorithm. Moreover, s alability
applies to memory usage as well, as dis ussed in (i).
b

58

lines of ode). The lass wavefun tion ontains the k-point at whi h the wave fun tion is
de ned, the number of bands and plane waves kept, the wave fun tion oe ients and energies. Moreover, it ontains basi operations su h as time reversal, onvolution, and Fourier
transform. These basi operations are written in a general manner su h that they apply not
only for the onstru tion of the matrix elements of the independent-parti le polarizability
[ f. Eq. (101) from the wave fun tions. They an be used as well for the plasmon-pole
eigenve tors (also of type wavefun tion) and the onstru tion of the self-energy expe tation values [ f. Eq. (106).
f. E ien y
Sin e C++ is less well established in the s ienti ommunity than Fortran an interfa e with
existing Fortran odes su h as low-level BLAS subroutines is a must. E ient ode results,
for example, from interpreting wave fun tions as matri es rather than as linear arrays and by
performing onvolutions as in Eqs. (101) and (106) via BLAS3 matrix multipli ations. As a
onsequen e, major portions of the ode run at about 270 MFlops on a CRAY-YMP8 (peak
performan e 333 MFlops). The overall ode performan e is 170 MFlops and, in addition,
the ode uses memory very e iently a ording to the standard CRAY performan e tools.
About 20% of the program is do umentation to make it easy to maintain and use.
A good test of the reliability of a ode is a \standardized" test al ulation and omparison with an independently written ode. To eliminate subtle di eren es in pseudopotentials,
parametrization of ex hange- orrelation potentials, and the like, whi h plague input to selfenergy al ulations using di erent LDA odes, one an generate wave fun tions and energies
using an empiri al Si pseudopotential [331 instead. The orresponding wave fun tions and
energies are, in addition, easy to generate. Results based on empiri al pseudopotentials between two independent odes from Refs. [42, 302 agree to within nine signi ant digits.

57

to identify the pro edures, i.e., the data manipulations, required to solve a problem and the
orresponding best algorithms. The stru ture element of a pro edure-oriented ode is the
pro edure or subroutine with its input and output data. This way of programming leads in
general to many global and only few lo al data. The global data are either passed expli itly
from subroutine to subroutine or { as in Fortran { passed by using COMMON blo ks. This
violation of the software engineering prin iple of data lo ality [327 an lead to severe problems on e a omplex pie e of software has to be debugged, modi ed, or extended beyond
the realm of its initial use [328.
An obje t-oriented programming paradigm [329 on eives the task of solving a omputational problem as identifying intera ting lasses or obje ts. A lass is an abstra t data type
or a user-de ned data type. It omprises data and all operations ne essary to manipulate
the data. For instan e, the abstra t data type VECTOR is the ensemble of the operations that
reate, destroy, and manipulate (s alar and ve tor multipli ation, addition, et .) a ve tor,
an integer orresponding to the ve tor length, and a pointer to its rst element.
Classes onsist of a header le that de lares the lass type { i.e. its data members and
member fun tions { and a le ontaining the a tual implementation of the lass fun tions.
A software user should be able to use a lass e iently in a parti ular appli ation by looking
only at the header le. Details of the representation of the data as well as algorithms used
for a parti ular numeri al problem are hidden from the user. Moreover, unauthorized user
a ess to lass data is prohibited. This prin iple of data hiding or information hiding redu es
the use of global variables and leads to the design of reusable, lo al program modules with
en apsulated data.
Classes as program modules should be written in a reusable and general way. For instan e,
a lass VECTOR should not be limited to ve tor-ve tor operations but should also allow matrixve tor operations. Note that the prin iple of inheritan e an in rease the reusability of
ode onsiderably. The basi idea of inheritan e is that ommon features of two di erent
lasses are in orporated into a base lass whose properties are then inherited by the so alled derived lasses. For example, onsider a base lass HUMAN with private data AGE and
WEIGHT and member fun tions EAT, DRINK, and SLEEP. A derived lass STUDENT would ontain
all the fun tionalities of HUMAN but on top of it the member fun tions ATTEND LECTURE,
DO HOMEWORK, and GOOF OFF.
The re ipro al-spa e GWA ode of Ref. [42 is written in C++ in an obje t-oriented style.
Data abstra tion at a low-level is a hieved through extensive use of an in-house C++-library
that de nes the abstra t data types VECTOR and MATRIX [330. At a higher level, the entral
lasses of the ode are symmetry, selfenergy, polarizability, and wavefun tion. To
des ribe data en apsulation and ode reusability onsider symmetry and wavefun tion as
examples. The lass symmetry an urrently handle zin blende materials su h as GaAs and
elemental semi ondu tors su h as Si. However, it provides the full fun tionality (apply a parti ular symmetry operation, nd its inverse and apply the inverse, determine the little group
of a ve tor, et .) irrespe tive of the spa e group under onsideration. Treating a system
with, e.g., wurtzite symmetry therefore requires only hard oding of the orresponding symmetry operations in the implementation of symmetry (about 150 lines out of a total of 10000
56

the logarithm of the relative deviation of the quantity to be onverged E from its onverged
value E1 as a fun tion of the onvergen e parameter N is roughly linear [322, i.e., with
being a onstant
log10

E1 E 
 N
E1

) E = E1

1 10

(122)

The numeri al ut-o s used for Si as well as ut-o s resulting from onvergen e studies of
the other four materials that are onsidered in Se tion 18 are summarized in Table 18.
Convergen e properties di er from material to material and have to be repeated for every
material under onsideration. Convergen e studies as a fun tion of the energy ut-o and the
number of k-points are ostly, sin e a new plasmon-pole band stru ture has to be generated
ea h time. Often onvergen e studies an be limited to two and ten spe ial k-points. An
appropriate energy ut-o an be determined by hoosing it large enough to onverge LDA
valen e and low-lying ondu tion band energies to within 50 meV. For example, for Si an
in rease in energy ut-o from 8.5 to 18 Hartree hanges the LDA energies of the valen e and
the four lowest ondu tion bands at , X , and L by less than 80 meV and the orresponding
quasiparti le energies (shown in Table 17) by less than 0.1 eV.
d. Choi e of pseudopotentials and plasmon-pole models
Di eren es in pseudopotentials an in uen e LDA band stru tures by about 0.1 eV for states
lose to the band gap. Hybertsen and ollaborators [5, 44 use Kerker pseudopotentials [323,
Godby et al. [6, 185, Rohl ng et al. [52, 114 and Ba kes et al. [130 use Ba helet{Hamann{
S hluter pseudopotentials [324, and Ref. [42 uses soft Troullier-Martins pseudopotentials
[325. Deviations for well- onverged LDA and GWA al ulations from di erent authors
of about 0.1 to 0.2 eV are to be expe ted. Table 19 estimates the in uen e of the pseudopotential hoi e on GWA al ulations by omparing quasiparti le energies obtained with
a Troullier-Martins pseudopotential [325 with energies obtained for a generalized norm onserving pseudopotential [326. Deviations between the LDA and GWA al ulations using
both pseudopotentials do not ex eed 0.2 eV for both the valen e and low-lying ondu tion
bands. Corresponding deviations for self-energy shifts are 60 meV or less.
Table 20 ompares Si quasiparti le energies obtained using the von der Linden{Hors h
and the Engel{Farid plasmon-pole models and shows that the hoi e of di erent plasmon
pole models hanges quasiparti le energies by 0.1 eV or less. This agrees with the ndings
of Northrup et al. [184 who nd only small di eren es in the band stru ture of nearlyfree-ele tron metals using the Hybertsen{Louie model ompared to an earlier al ulation by
Lundqvist [98 that uses a di erent plasmon-pole model.
e. Obje t orientation
The ommon omputing paradigm in most s ienti appli ations is pro edure-oriented programming. The entral task of a software engineer using the pro edure-oriented paradigm is
55

b. Integration of the Coulomb singularity


The expe tation value of the self-energy ontains sums over umklapp pro esses whose G = 0
ontribution has an integrable 1=jqj2 divergen y for q ! 0. Consider the ase [317 of X
and let f (q) be a smooth fun tion that diverges as 1=jqj2 for q ! 0 and whose integral over
the Brillouin zone is known analyti ally. Rewrite the expe tation value of X as [90

o X M vl (k; q)[M vm (k; q)


BZ X
4 X
G
G
=
V q v G
jq + Gj2
BZ
o
X
4 X
vl vm f (q):
V v
q
"

j jl; ki

m; k X

vl vm f (q)
(119)

The term in square bra kets is no longer singular at q = 0 and an be integrated using
spe ial points. The last term is integrated analyti ally. Possible hoi es for f (q) for f
symmetry are (a = latti e onstant, V = unit ell volume) [90
(a=2)2
f (q) =
;
3 os(aqx =2) os(aqy =2) os(aqy =2) os(aqz =2) os(aqz =2) os(aqx =2)

a 2
V Z
4:423758;
(120)
f (q)dq =
(2 )3 BZ
2
p
and with  as the step fun tion and b = jqL j = 3=a [318

f (q) =

2 (1 + os(

2j q j

 jq j
))(b
b

jq j) ;

V Z
V
f (q)dq = 2 b:
3
(2 )
(2 )

(121)

Chosing either Eq. (120) or (121) for f (q) leads to deviations in the valen e and low-lying
ondu tion quasiparti le energies of Si and Ge at , X , and L of less than 30 meV. Fun tions
f (q) appropriate for other symmetries than f have been suggested by Wenzien, Cappellini,
and Be hstedt [319.
. Convergen e
Quasiparti le band stru tures an vary by a few hundreds to a few tens of a meV due to
di eren es in (i) the number of q-points used in the integration of Eqs. (104) and (105),
(ii) the energy ut-o used in the expansion of the LDA wave fun tions, (iii) the number
of single-parti le and plasmon-pole bands kept in the summations in Eq. (105), (iv ) the
number of G-ve tors kept in the summation in Eq. (106), and (v ) the degree of onvergen e
of the plasmon-pole band stru ture. To determine reliable quasiparti le band stru tures all
these numeri al ut-o s have to be he ked systemati ally. Convergen e with respe t to the
numeri al ut-o s mentioned in (i) (iv ) is generally smooth [320 as an be inferred from
Figs. 24-27 and Table 17. Details of the al ulations are given in the aptions. A plot of
54

16. PLANE WAVES: NUMERICAL DETAILS


This se tion has a threefold purpose: (i) Detailed information on the use of symmetry and
the integration of the Coulomb divergen e in a tual GWA implementations (see parts a and
b) is presented. (ii) The e e ts of di erent numeri al parameters on quasiparti le energies
in plane-wave-based GWA al ulations are spe i ed (see parts and d). (iii) Details about
a parti ular GWA implementation are provided (see parts e and f).
a. Use of symmetry
The spe ial k-points te hnique [315 redu es by symmetry the summation over a uniform
mesh of k-points needed to integrate the independent-parti le polarizability (Eq. 102)) and
the self-energy (Eqs. (104) and (105)) over the Brillouin zone to the summation over a smaller
set of spe ial k-points. With S as an element of the little group Lq of the external wave
ve tor [316, i.e., S q = q, and S as its non-symmorphi translation, the matrix elements of
Eq. (101) an be written as [81
MGv (S 1 k; q) = exp(i(q + S G)  S )MSv G (k; q):
(115)
With BZq as irredu ible part of the Brillouin zone de ned by the little group of q the stati
independent-parti le polarizability (Eq. (102)) is given by [81
q
X
X
4 X BZ
0
PGG (q) =
exp(i(S G S G0 )  S )MSv G (k; q)[MSv G (k; q) ;
("vk q " k) 1
V ;v k
S 2Lq
(116)
where the ontribution from ea h k-point in the BZq is multiplied by an appropriate weight.
The use of symmetry redu es the omputational demand onsiderably for q-points along
high-symmetry dire tions. For instan e, 256 k-points in the full zin blen e ( ubi ) Brillouin
zone an be redu ed to 40 for q parallel to qX and to 60 points for q parallel to qL . Care
has to be taken to add up the phase fa tors in the above equation orre tly.
The external waveve tor k for X and C (E ) determines the Brillouin zone BZk that is
relevant for the integration of the self-energy in re ipro al spa e. Appli ation of the elements
of the little group of k to Eqs. (104) and (105) leads to a an ellation of phase fa tors and
the following expressions for X and C (E )
o X BZ
k M vl (k; q)[M vm (k; q)
X
X
G
G
(117)
hm; kjX jl; ki = 4V
j
q
+
G
j2
v G q
P M BZ
o +
uno PX
k
X
X
pnm (k; q)[ pnl (k; q)

hm; kjC (E )jl; ki = V1
E "n;k q + !p(q)sgn( "n;k q)
q
p
n
(118)
where = 2zpq!p (q) for the von der Linden{Hors h and = 1 for the Engel{Farid plasmon pole model.
0

53

. The independent-parti le polarizability


The independent-parti le polarizability [312 an be determined in real spa e and imaginary
time by an O(NP W ) operation ( ompare Eq. (24))
P 0 (r; r0 ; i ) = iG0 (r; r0 ; i )G0 (r; r0; i ):
(112)
However, the diele tri matrix and the s reened intera tion require onvolutions in real spa e
(Eqs. (31) and (25)) but multipli ations in re ipro al spa e (Eqs. (34) and (27)). It is easier to
onstru t these quantities in re ipro al spa e and as a fun tion of imaginary frequen y whi h
requires a Fourier transformation of P 0 (r; r0; i ). The spatial Fourier transforms require
spe ial are sin e P 0 is not translationally invariant in the 6-dimensional spa e spanned by
r and r0 . In the following equations, we do not exhibit the time/frequen y dependen e for
simpli ity and de ne P 0 (k; r; r0) { where both r and r0 are in the real spa e unit ell { as

P 0 (k; r; r0) =

IC
(r)
X
R

exp( ik  (r

r0

R))P 0 (r; r0 + R):

(113)

The sum over latti e ve tors R is limited to ve tors in the intera tion ell of r (IC (r)).
The quantity P 0 (k; r; r0) is periodi in r and r0 separately and its Fourier transform an
be determined by two su essive 3-dimensional FFTs [313. The Fourier transform of the
independent-parti le polarizability is given as (V is the unit ell volume) [314
0 (k) = 1
PGG
0

Z Z

V V

exp( iG  r)P 0(k; r; r0) exp(iG0  r0 )drdr0:

(114)

On e P 0 is determined in re ipro al spa e and imaginary time, the determination of


the diele tri matrix and the s reened intera tion redu es to matrix multipli ations and
inversions whi h s ale as the third power of the matrix size. The a tual omputation is not
dominated by this part of the algorithm sin e the dimension of the diele tri matrix an be
hosen to be mu h smaller than the number of points in the real spa e unit ell.
The self-energy must be al ulated in real spa e and imaginary time to avoid onvolutions.
Therefore, the s reened intera tion W must be Fourier transformed from re ipro al spa e
and imaginary frequen y to real spa e and imaginary time, with areful onsideration of the
long-range part of W [103. Expe tation values of the self-energy operator hnk j(i! )jnki
an then be determined after Fourier transformation of  from imaginary time to imaginary
frequen y. The analyti stru ture of G and W di tates that the self-energy has poles in the
se ond and fourth quadrant of the omplex plane. One an therefore analyti ally ontinue
the self-energy from the negative (positive) imaginary frequen y axis to the negative (positive) real frequen y axis without rossing any bran h uts. This analyti ontinuation is
a hieved by tting the self-energy along the imaginary frequen y axis to a multipole fun tion
[103.
52

fun tion from real to imaginary energy and Fourier transformation results in [307

G0 (r; r0; i ) =

 0
i o
nk nk (r)nk (r ) exp("nk  );  > 0:
Puno
i nk nk (r)nk (r0 ) exp("nk  );  < 0:
P

(108)

In this approa h, r denotes a point in the irredu ible part of the real spa e unit ell while r0
denotes a point in the \intera tion ell" outside of whi h G0 is set to zero. Denote as unk(r)
the periodi part of the Blo h wave fun tion nk (r) and de ne for a given r a ve tor r00 in
the real spa e unit ell and a real spa e latti e ve tor L su h that [308
r0

= r + r00 + L  r + x;

= r00 + L:

(109)

unk (r)unk(r + r00 ) exp( ik  x) exp("nk ):

(110)

Then

G0 (r; r + x; i ) = isgn( )

o (X
uno )
nk

Note that  is positive or negative depending on whether the sum is over o upied or uno upied states, respe tively. Finally, write the sum over k-points in the full Brillouin zone (BZ)
as a sum over k-points in the irredu ible Brillouin zone (IBZ) and over symmetry operations
S that generate the k-points in the full BZ. One obtains the following formula for G0 whi h
is implemented in the real-spa e/imaginary-time program

G0 (r; r + x; i ) = isgn( )

o (X
uno ) IBZ
X X
n

unk(S 1 r)unk (S 1 (r + r00)) exp( iS k  x) exp("nk ):

(111)
Assuming an intera tion ell that is of onstant size for a given material, the determination
of the independent-parti le propagator s ales as N!  Nband  Nr where N! is the number
of frequen ies or times onsidered, Nband the number of bands in the summation of the
above equation, and Nr the number of r-points in the real spa e unit ell. Sin e Nband
and Nr in rease linearly with the size of the system, the overall s aling of the method is
proportional to the system size squared and hen e of order O(NP2 W ).
Convergen e onsiderations. Convergen e parameters that are important for the real
spa e approa h are (i) the number of bands in Eq. (111), (ii) the real-spa e grid spa ing r
and the size of the intera tion ell, and (iii) the time spa ing  and the maximum sampling
time max . Convergen e to within 20 meV for Si requires 145 bands, a r  0.32 a.u., an
intera tion ell radius [309 Rmax  18 a.u., a time spa ing   0.15 a.u., and max  20
a.u. This orresponds to 170 r-points in the irredu ible wedge of the real spa e unit ell and
to Nr  (4=3)(Rmax =r)3  0:75  106 points in the intera tion ell [310. The propagator G0 (r; r0;  ) requires 0.8 MW storage for every r and ea h of the max = = 130 time
points. Storage requirements for the algorithm are therefore large despite the nite range
of the intera tion ell and may be ome a bottlene k of the al ulation for larger systems [311.
0

51

b. Real-spa e/imaginary-time approa h


The basi idea of the spa e-time approa h is to hoose the representation (e.g. re ipro al
spa e and frequen y or real spa e and time) that minimizes the omputations ne essary to
evaluate the basi GWA quantities: G, ", W , . For example, the determination of the
self-energy in re ipro al and frequen y spa e, Eqs. (104) and (105), involves numeri ally
expensive onvolutions whi h lead to an overall s aling of the algorithm proportional [306
to NP4 W and to N!2 , the square of the number of mesh points used for the representation
of the frequen y dependen e of the s reened intera tion. In real spa e and as a fun tion of
time, the self-energy is a simple produ t ( ompare Eq. (22))
(r; r0 ;  ) = iG(r; r0 ;  )W (r; r0;  )

(107)

whi h eliminates two onvolutions in re ipro al spa e and one in the frequen y domain and
leads to an algorithm whose dominant parts s ale as O(NP2 W ) and O(N! ). Similarly, the
diele tri matrix and the s reened intera tion require onvolutions in real spa e (Eqs. (31)
and (25)) but multipli ations in re ipro al spa e (Eqs. (34) and (27)). A representation
hange from re ipro al to real or frequen y to time spa e using Fast Fourier Transforms
(FFTs) and vi e versa s ales as NP W log(NP W ) or N! log(N! ) and is omputationally very
e ient. This allows the e ient determination of , ", and W as produ ts rather than as
onvolutions.
The evaluation of operators in real spa e and the extensive use of FFTs requires (i)
operators that are short-ranged in real spa e, and (ii) quantities that an be represented
by an equidistant numeri al grid. Relevant quantities in GWA, namely G, , and P 0 , are
proportional to jr r0 j 2 for jr r0 j ! 1 and indeed short-ranged ( ompare for example
Figs. 9 and 11). The s reened intera tion de ays proportional to jr r0 j 1 for jr r0 j ! 1
but this long-range tail an be taken into a ount expli itly [103 allowing the use of a
nite ut-o for jr r0 j in numeri al work. Although G, , and W have bran h uts on
the real frequen y axis, they an be analyti ally ontinued to the imaginary-frequen y (and
imaginary-time) axis along whi h they are mu h smoother and an be a urately dis retized
by an equidistant Fourier grid as shown in Fig. 23.
The entral task of the real spa e/imaginary time algorithm is the same as in the re ipro al spa e/frequen y spa e algorithm: Determination of G ! P 0 ! " ! W !  and
subsequent al ulation of quasiparti le shifts and if desired the solution of Dyson's equation.
Here, we will des ribe the onstru tion of G and P 0 and the Fourier transformation of P 0
in detail, sin e their onstru tion is used to illustrate the parallel real spa e/imaginary time
algorithm in Se tion 17. For further details and onvergen e studies we refer the reader to
the work by Rieger et al. [103.

: The Green fun tion


Analyti ontinuation of the spe tral representation (Eq. (15)) of the non-intera ting Green
50

ati ally onverge, onstru ting su h basis sets is di ult. Table 15 demonstrates the problems in establishing the energies of low-lying ondu tion states of small-gap and medium-gap
semi ondu tors. For bulk semi ondu tors, 20 Gaussians per atom are suggested to be adequate for onvergen e of quasiparti le energies of low-lying ondu tion and valen e states
to within 0.1 eV [114. While this is true for Si [114 and for large-gap materials with
strongly lo alized densities su h as diamond, SiC, and GaN [295, good onvergen e for
more \metalli ," small- and medium-gap semi ondu tors su h as Ge and GaAs requires at
least 30 Gaussians per atom. Tables 15 and 22 show that in the ase of Ge (i) the lowest
ondu tion band energies at , X , and L for a well- onverged [296 plane-wave and a 40Gaussian-orbital al ulation di er by up to 0.3 eV in LDA and up to 0.6 eV in GWA, (ii)
higher-lying states su h as the L02 state di er by up to 1.3 eV in LDA and 1.6 eV in GWA,
and (iii) the Gaussian-orbital results onverge systemati ally towards the plane-wave results
when 60 Gaussians rather than 40 Gaussians are used. Similar on lusions an be drawn
from Tables 15 and 23 for GaAs. In parti ular, the di ulty to des ribe low-lying ondu tion
states at X and L with only 40 Gaussians may result from an enhan ed d hara ter of these
states [297.
The problem of properly treating d states near the valen e band is illustrated by the
work on CdS [52. As pointed out in Se tion 12, semi ore d states modify dynami s reening
in a solid [43, 52, 201. In addition, the ex hange intera tion between all ele trons of a
shell (n = 4 in CdS) a e ts the energies of semi ore and valen e ele tron states [52 if the
orresponding wave fun tions overlap strongly [298. Quantitative results for CdS are di ult
to obtain sin e CdS seems to be sensitive to the pseudopotential used. As shown in Table 16
treating the Cd 4d ele trons [196 as ore ele trons, via non-linear ore orre tions [205, or
as valen e ele trons gives LDA energy gaps of 1.72 eV, 1.60 eV, and 0.84 eV, respe tively,
for s alar-relativisti Troullier-Martin pseudopotentials in the Kleinman-Bylander form [304.
Semi-relativisti , non-lo al ab-initio pseudopotentials [51 give an energy gap of 1.36 eV when
non-linear ore orre tions are used (E ut = 12.5 Hartree) and s alar relativisti Ba helet{
Hamann{S hluter pseudopotentials [301 give an energy gap of 1.65 eV when the d ele trons
are treated as ore ele trons and of 0.3 eV when the d ele trons are treated as valen e
ele trons [305. Using the s alar-relativisti Ba helet{Hamann{S hluter Cd pseudopotential
in Refs. [52 and [302 gives an LDA energy gap of 2.15 eV and 2.18 eV, respe tively, when
the d ele trons are treated as ore ele trons. An energy gap of 0.78 eV is obtained when they
are treated as valen e ele trons [52. The deviations in the fundamental LDA energy gap
between the al ulations of Refs. [51, 196, 301 and those of Refs. [52, 302 using di erent
Cd2+ pseudopotentials amount to at least 0.5 eV and are on the order of the self-energy
shifts observed upon in lusion of 4p and 4s ele trons as valen e ele trons [52.
Good quasiparti le band gaps are obtained by treating the ore and semi ore ele trons in
II-VI materials via non-linear ore orre tions [51. However, the su ess of this approa h is
based on a fortuitous an ellation of errors due to (i) the negle t of wave fun tion relaxation
and hybridization, and (ii) negle t of dynami s reening by semi ore ele trons and ex hange
intera tion with ore and semi ore ele trons.
49

very large energy ut-o and several thousand plane waves. In LMTO, the des ription of
transition-metal oxides uses only 50-100 basis fun tions per atom [55.
Aryasetiawan, Gunnarsson, and ollaborators [14 use LMTO in the atomi sphere approximation and in lude so- alled ombined orre tions [289 only in the energies but not
in the wave fun tions [290. This approa h has two disadvantages: (i) Omission of the
ombined- orre tion term leads to dis ontinuous wave fun tions in the interstitial region
and in the overlapping region of the mun-tin spheres [291, 292. This pro edure results in
errors in the determination of the matrix elements of the momentum operator and hen e,
for instan e, in the diele tri properties and subsequently the self-energy operator. (ii) The
atomi sphere approximation assumes a spheri ally symmetri potential. This shape approximation an a e t properties su h as the diele tri onstant. For instan e, Christensen
and Gor zy a [193 determine the diele tri onstant of GaN within the atomi sphere approximation in luding ombined- orre tion terms to 4.78, a 20% underestimation ompared
to the full-potential LMTO value of 5.96 [293.
An estimate of the in uen e of the above approximations on quasiparti le energies is
di ult. Insight an be gained by omparing all-ele tron LMTO results for GaAs [290 with
pseudopotential results that in lude ore-polarization potentials and ore relaxation e e ts
[43 as well as with experiments. Shirley and ollaborators obtain quasiparti le orre tions
of 1.29/0.74/1.05 eV for the lowest ondu tion band at , X , and L ompared to values of
1.19/1.59/1.42 eV using s alar relativisti LMTO [290 as an be inferred from Table 23.
LMTO quasiparti le orre tions are larger than the best plane wave results by 0.1 to 0.8
eV. In addition, LMTO in the atomi sphere approximation overestimates the low-lying
experimental ondu tion band energies by 0.3 to 1.1 eV as shown in Table 23. Note, that the
LMTO al ulation of Ref. [290 hooses a trial energy around whi h it makes an expansion.
This trial energy is hosen to a urately desribe the valen e and semi ore states of GaAs
while less emphasis is pla ed on uno upied states. The o upied states are indeed a urately
des ribed in LMTO while the des ription of the uno upied states is substantially worse.
Choosing several referen e energies an improve the des ription of uno upied states [290.
Note that Kubo's al ulations [287, 288 avoid the above mentioned problems by evaluating
the GWA based on a full-potential LMTO al ulation [294.
Gaussian orbitals. Baroni and ollaborators [140, 141 use a ontra ted Gaussian orbital
basis set to determine the ele troni properties of ore and valen e ele trons in the COHSEX
approximation (see Se tion 9). More re ently, Rohl ng, Kruger, and Pollmann [52, 114,
284 developed an approa h for a GWA al ulation that is based on pseudopotentials in
onjun tion with an un ontra ted Gaussian-orbital basis set.
The merit of Gaussian-orbital-based GWA al ulations is the redu ed number of basis
fun tions and hen e their greater e ien y and appli ability ompared to plane wave al ulations as exempli ed by (i) a fa tor of ve speed up ompared to a plane wave al ulation
of the Si(001) (21) re onstru ted surfa e [284, (ii) an expli it treatment of the Cd n = 4
ore and semi ore ele trons [52, and (iii) the in lusion of ex itoni e e ts in Sin Hm lusters
[282.
The main disadvantage of Gaussian orbitals is that while Gaussian basis sets an system48

where the matrix elements are de ned as [277

pnm (k; q) =

[MGnm (k; q) pq(G);

(106)

and = 2zpq!p (q) for the von der Linden{Hors h and = 1 for the Engel{Farid plasmonpole model.
The NP4 W -s aling of the re ipro al-spa e GWA algorithm follows from Eqs. (101), (105),
and (106). The onstru tion of the matrix elements in Eq. (101) s ales as the number of
plane waves used to des ribe the LDA wave fun tions. The matrix elements in Eq. (106) are
determined in NG operations where NG is the number of plane waves used to des ribe the
plasmon-pole eigenve tors. The self-energy itself (Eq. (105)) must be determined via a sum
over LDA bands and a sum over plasmon-pole bands. The number of LDA and plasmon
pole bands as well as NG and NP W in rease linearly with system size and are all of the same
order. Hen e the overall algorithm s ales as the size of the system or the number of plane
waves to the fourth power. An approximate evaluation of the self-energy [278 via Taylor
expansions around a given set of energies redu es the GWA s aling to NP3 W and allows larger
GWA al ulations based on plane waves. Other approa hes [279, 280 permit the determination of the density-density response fun tion with an O(NP3 W ) e ort, but have not been
extended to the al ulation of the self-energy.

. Lo al-orbital basis sets


The number of basis fun tions of lo al-orbital basis sets [15, whi h is needed to des ribe bulk
semi ondu tors, is smaller by about one order of magnitude than the orresponding number
of plane waves [281. Although the overall s aling of the re ipro al-spa e GWA algorithm
still s ales as the number of basis fun tions to the fourth power, the strong redu tion of the
number of basis fun tions results in signi ant savings in omputation time and allows the
study of materials that are not a essible in plane-wave-based approa hes su h as NiO [55
or Sin Hm lusters [282. Unfortunately, the matrix element onstru tion is omputationally
more intense in a lo al-orbital than in a plane-wave basis whi h partially redu es gains due
to the smaller number of basis fun tions [283.
Linearized Augmented Plane Waves (LAPW). LAPW is an all-ele tron method that has
been applied to GWA al ulations in Si [285 and Ni [68. In Si, 45 basis fun tions per Si
atom are needed whi h orresponds to a redu tion by a fa tor of ve ompared to plane-wavebased al ulations. Although LAPW al ulations allow systemati onvergen e, they do not
seem to o er signi ant omputational savings ompared to plane-wave-based al ulations
whi h may have inhibited a wide-spread use of LAPW for GWA al ulations [286.
Linearized Mun Tin Orbitals (LMTO). LMTO is an all-ele tron method that has been
used for instan e for GWA al ulations of transition-metal oxides [55 and the Compton
pro le of alkali metals [287, 288 and is extensively reviewed in Ref. [14. GWA al ulations
for transition-metal oxides are prohibitively expensive for plane-wave-based methods sin e
an a urate des ription of the transition-metal d and oxygen 2p ele trons would require a
47

in terms of its Fourier omponents nk (G), G is a re ipro al latti e ve tor, as


1 X
nk (G) exp(i(k + G)  r):
nk (r) = p
V G

(100)

De ne the following matrix element between o upied valen e (n = v ) and uno upied
ondu tion (n = ) states

M v (k; q)
G

vk q (r) exp( i(q + G)  r) k (r)dr

vk q (G0

G) k (G0 ):

(101)

The independent-parti le polarizability given by Eq. (33) is


0 (q; ! ) =
PGG
0

2
V

o uno BZ

X X X

"v k

MGv (k; q)[MGv (k; q)


0

" k

! + i

"vk

" k + ! + i

(102)

where the fa tor 2 a ounts for spin degenera y.


The frequen y onvolution in Eq. (35) together with the independent-parti le Green
fun tion (Eq. (15)) expressed in terms of Blo h wave fun tions and the Fourier omponent
of the s reened intera tion WGG (q; ! ) allow the determination of the matrix elements of
the self-energy with respe t to Blo h states mk  jm; ki and lk  jl; ki as the following
sum over o upied and uno upied states
BZ X
o +
uno X
X
hm; kj(E )jl; ki = V1
MGnl (k; q)[MGnm (k; q)
q GG
n
Z 1
i! )
WGG (q; ! )
 1 exp(
d!: (103)
( 2i) E + ! "nk q i sgn( "nk q)
0

Here, the matrix elements MGnm (k; q) generalize Eq. (101) to arbitrary states n and m.
The remaining frequen y integration is usually performed analyti ally using the plasmonpole models presented in Se tion 8 b rather than numeri ally as in Refs. [102, 103, 185, 276.
The plasmon-pole model (PPM) is a urate to within a few tens of a meV for states lose
to the Fermi level and to within a few tenths of an eV for low-lying valen e states as is
demonstrated in Table 21. Splitting the self-energy into a bare ex hange part X and an
energy-dependent orrelation ontribution C (E ), as detailed in Se tion 6, gives

hm; kjX jl; ki


hm; kjC (E )jl; ki

BZ X M vl (k; q)[M vm (k; q)


o X
4 X
G
G
;
(104)
V v q G
jq + Gj2
PM
uno PX
BZ o +
X
pnm (k; q)[ pnl (k; q)
1X

=
; (105)
V q
E "nk q + !p(q)sgn( "nk q)
p
n

46

III. GWA al ulations: Numeri al onsiderations


This hapter (i) des ribes various re ipro al-spa e and real-spa e/imaginary-time implementations of the GWA, (ii) gives numeri al details for an implementation of the GWA
in a plane-wave basis, (iii) des ribes parallel algorithms of GWA al ulations in re ipro al
spa e as well as in real spa e/imaginary time, and (iv ) ompares GWA al ulations for ve
prototypi al semi ondu tors.
15. DIFFERENT IMPLEMENTATIONS OF THE GWA
Quasiparti le al ulations an be performed either in re ipro al spa e as a fun tion of frequen y or in real spa e as a fun tion of imaginary time. Both approa hes are des ribed in
this se tion; part a ontains the re ipro al-spa e and part b the real-spa e approa h. The
re ipro al-spa e method is urrently widely used and has been implemented using plane
waves as well as a variety of lo al-orbital-basis sets. Part a ontains a omprehensive omparison of the advantages and weaknesses of the di erent basis sets.
a. Re ipro al-spa e approa h
Early al ulations [5, 6 in the dynami ally s reened potential approximation determine the
expe tation value of the self-energy operator using a plane wave basis set in re ipro al and
frequen y spa e sin e this allows both a straightforward evaluation of matrix elements that
o ur in the self-energy and a systemati ontrol over onvergen e. In addition, a GWA al ulation in re ipro al and frequen y spa e parallels the experimental situation in (inverse)
photoemission whi h determines the band stru ture of a solid as a fun tion of the re ipro al
wave ve tor k and of the frequen y ! of the quasiparti le.

. Plane waves
General remarks. Pseudopotentials in onjun tion with a plane-wave basis set are widely
used in omputational ondensed matter theory due to their ease of use and systemati
onvergen e properties [275. Mostly, plane-wave-based GWA al ulations are applied to
sp-bonded bulk solids and to their interfa es, surfa es, defe ts, and lusters as is dis ussed
in Chapters IV and V.
The two main disadvantages of plane-wave basis sets are (i) the number of plane waves
NP W in reases with the system volume V and the energy ut-o E ut needed for a on3=2 (in Hartree atomi units), and (ii) plane waves
verged des ription as NP W  (1=21)V E ut
have no dire t physi al interpretation in ontrast to lo al-orbital basis sets dis ussed below.
Re ipro al-spa e GWA al ulations s ale as NP4 W (see below) whi h auses plane-wave-based
GWA al ulations for large-V systems su h as ompli ated defe t stru tures and for largeE ut systems su h as d and f ele tron materials to be prohibitively expensive.
Detailed formulas. A Blo h wave fun tion of wave ve tor k and band n an be expressed

45

to RPA s reening by 0.1 eV (0.2 eV) for Si (diamond), (iv ) a signi ant in rease of the
absolute value of the diagonal polarizability matrix elements ompared to RPA by vertex
orre tions, and (v ) a signi ant de rease of the same matrix elements by self- onsisten y
e e ts leading to large an ellations and an overall in rease of the matrix elements by  15%
ompared to RPA, The diagrams that are al ulated for the diele tri polarizability and the
self-energy are shown in Fig. 21. The solid lines in these diagrams orrespond to a singleparti le propagator whi h is onstru ted from LDA wave fun tions and energies. The wiggly
lines orrespond to the s reened intera tion whose frequen y dependen e is modeled by the
Engel{Farid plasmon-pole model [271. The results of adding the lowest-order vertex (V)
and self-energy (SC) orre tions to the RPA polarizability are shown graphi ally in Fig. 22.
Both the vertex and the self- onsisten y orre tions to the RPA polarizability are nite for
k ! 0 and only their sum tends to zero proportional to k 2 . This proportionality for the
head of the stati polarizability is ne essary to ensure the orre t s reening behavior of a
semi ondu tor in the long-wavelength limit [119, 272 and provides a formal motivation for
an in lusion of both e e ts in the polarizability. The e e t of the vertex and self- onsisten y
orre tions on the diele tri onstant within the approximations by Ummels et al. [119
amounts to 20% in the ase of Si and to 5% in the ase of diamond [273 and is therefore
at least as important as lo al- eld e e ts due to an inhomogeneous density distribution.
In lusion of vertex and self- onsisten y orre tions in the self-energy leads to an in rease
of fundamental band gaps by 0.4 eV (0.3 eV) in Si and 0.7 eV (0.5 eV) in diamond using
RPA+V+SC (RPA) s reening [119. Band gaps determined using di erent ombinations of
vertex and self- onsisten y orre tions for the polarizability and the self-energy are shown
in Table 14. The in uen e of V+SC orre tions to the self-energy operator leads to a signi ant in rease in fundamental band gaps. The results of Ummels et al. [119 suggest that the
an ellation between lowest-order vertex and self- onsisten y ontributions is far from being
omplete if one determines these orre tions to the GWA self-energy using a non-intera ting
LDA Green fun tion. In fa t, the V ontribution an els the SC ontribution to the selfenergy by only 35% (45%) in the ase of Si and only 10% (15%) in the ase of diamond for
RPA+V+SC (RPA) s reening. In the latter ase, even the term \ an ellation" is therefore
inappropriate [119.

44

Vertex orre tions and the alkali metal band width. In jellium and simple metals, bandwidth orre tions due to vertex orre tions to the polarizability P and to the self-energy 
an el, leading to a reprodu tion of RPA results as shown in Fig. 20 and an overestimation
of the experimental band width. The dis repan y with experiment an be eliminated by
(i) in lusion of vertex orre tions in only the polarizability, i.e., use of a GWKx approa h,
and self- onsistent determination of quasiparti le energies [184, 258, (ii) areful treatment of
surfa e and nite life time e e ts [229, 240, 241, 265, and (iii) in lusion of vertex orre tions
in both P and  in a partially self- onsistent al ulation [232. Approa h (i) is motivated
by Ward-identity-like arguments by Strinati et al. [156 (see Se tion 9 b). Mahan and
ollaborators [240, 241, 265 and Ting, Lee, and Quinn [266 emphasize that a onsistent
way of handling vertex orre tions requires the in lusion of identi al vertex orre tions in P
and . Both ontributions an el to a large degree as shown in Fig. 20 leading to a bandwidth, whi h is nearly identi al to the one obtained in RPA and too large in omparison
with experiment. Vertex orre tions are negle ted in approa h (ii) [229. The required
band-width narrowing is obtained from a treatment of the inhomogeneous surfa e potential
and the nite imaginary part of the self-energy only. Shirley [232 ombines results from
partially self- onsistent GW0 A al ulations with stati vertex orre tions in P and dynami
se ond-order orre tions in  and suggests [232, 267 that dynami vertex orre tions for
 are more appropriate than the stati orre tions onsidered by Mahan et al. In spite of
the di erent physi s ontained in the respe tive approximations all three approa hes agree
with the experimental band widths (for example, 0.7 eV band-width narrowing in sodium
ompared to the free-ele tron result, see Se tion 26 b for more details). We estimate that
missing self- onsisten y e e ts ould in rease the band width of all of the above al ulations
by 0.4 to 0.7 eV based on the results of Holm and von Barth [231 for fully self- onsistent
GWA al ulations in jellium with rs = 4 (average Na density). This suggests, that the
interpretation of alkali metal photoemission spe tra is a di ult, not yet fully understood,
problem [268.
Vertex orre tions and partial self- onsisten y. Table 13 shows that the in lusion of
dynami vertex orre tions for  to se ond-order in W [232 virtually an els the results
of partial self- onsisten y. Vertex orre tions de rease the quasiparti le weight and the
band width and lead to a Fermi energy in worse agreement with the exa t solution for the
homogeneous ele tron gas. Overall, the results agree with those of a non-self- onsistent
GWKx al ulation whi h takes vertex orre tions for " into a ount via the following manybody lo al- eld fa tor f (q )
k2
f (q ) = Kx (n) 2 F 2 ;
(99)
kF + 0:08q
where Kx (n) is de ned as in Eq. (98) and where Vx (n) is the ex hange- orrelation potential
of a homogeneous ele tron gas with density n and Fermi momentum kF [269.
In lusion of lowest-order vertex and self- onsisten y e e ts beyond the RPA polarizability for Si and diamond [119 leads to: (i) a an ellation of the onstant ontributions to
the polarizability at k ! 0 of vertex and self- onsisten y orre tions, (ii) a signi ant modi ation of the diele tri onstant, (iii) an in rease in fundamental band gaps ompared

43

Vertex orre tions to se ond-order in the intera tion. The se ond-order ontribution
in the bare Coulomb intera tion to the self-energy and the energy gap of Si is negligible
ompared to the rst-order ontribution [88. In a bond-orbital approximation [19, 260 the
se ond-order terms an be written as the sum of two partially an eling ontributions [260:
(i) the partial blo king of ground-state orrelations within a bond upon addition/removal of
a parti le, and (ii) ex hange enhan ements of the polarization loud of the ele tron (hole)
for the bonds adja ent to the bond under onsideration. This suggests that se ond- and
higher-order e e ts have a negligible impa t on band gaps and an safely be negle ted.
However, vertex orre tions evaluated with a s reened rather than a bare intera tion lead
to a band-gap narrowing [261 of 0.26 eV at the point of Si, whi h amounts to 40%
of the standard GWA quasiparti le orre tion of about 0.7 eV [262. Although higher-order
orre tions are in luded in the self-energy they are negle ted in the polarizability in on i t
with Mahan's suggestion [10. The se ond-order ontribution partially an els the additional
band gap in rease of 0.7 eV due to self- onsisten y [230. E e ts due to the onsistent use
of vertex orre tions not only in the self-energy but also in the polarizability are dis ussed
in the paragraph Vertex orre tions and partial self- onsisten y.
LDA vertex orre tions. Extension of a standard GWA (GWRPA) al ulation for Si
[89 by in luding LDA mean- eld vertex orre tions in the polarizability (GWKx ) or in the
polarizability and the self-energy (GW ) shows that (i) relative energies are modi ed by
in luding vertex orre tions only in the polarizability, and (ii) an ellation between vertex
orre tions to the polarizability and to the self-energy o ur for relative but not for absolute
energy shifts. The GW approximation uses an LDA ex hange- orrelation potential [263
as zeroth-order self-energy approximation and an be expressed in a GWA-like form using
~ and a diele tri matrix "~ [89
an e e tive ele tron-ele tron intera tion W
~ (1; 2)
(1; 2) = iG(1; 2)W
(97)

where

~ = v [1 P 0 (v + Kx ) 1 = v="~T ;
W
V (1)
"~ = 1 (v + Kx )P 0 ;
Kx (1; 2) = x :
(98)
n(2)
Table 12 shows that these vertex orre tions in luded only in the s reening redu e band gaps
by 0.1 to 0.2 eV and valen e band widths by about 0.5 eV in Si. Subsequent in lusion of
vertex orre tions in the self-energy ause a band gap in rease that an els the e e t of the
vertex orre tions in the s reening. Note the qualitative di eren e between this band gap
in rease [89 and the band gap de rease obtained by in luding dynami al vertex orre tions
in  [119, 262 as dis ussed in the paragraph Vertex orre tions to se ond-order in the
intera tion. Absolute energies between GWRPA and GW are shifted by about 0.4 eV.
Whereas in GWRPA the highest o upied state is shifted by 0.36 eV, it is shifted by only
+10 meV in GW . Sin e the highest o upied state is believed to be well des ribed by LDA,
GW ould turn out to be a better starting point, e.g., for valen e-band o set al ulations
at interfa es.
42

Early work on vertex orre tions in the homogeneous ele tron gas is not reviewed here
(for a general review, see Ref. [10). The present fo us is on work related to the e e t of
vertex orre tions [255 on the ele troni properties of insulators [89, 119 as well as on re ent
work on the homogeneous ele tron gas and simple metals [232, 240, 256, 257, 258.
Generally vertex orre tions have been studied for ex itations lose to the Fermi level.
Little is known about vertex orre tions of high-energy ex itations. This is unfortunate,
sin e the physi s of high and low energy ex itations an di er signi antly. An example is
the energy dependen e of the self-energy of Ag dis ussed in Se tion 26 a.
Two possibilities to in lude vertex orre tions beyond the standard GWA approa h are
urrently studied in the literature: (i) an iterative evaluation of Hedin's equations (Eqs. (21))
starting from Hartree theory [259, and (ii) an expansion of the self-energy  and the polarizability P to order n and n 1 in the s reened intera tion W , respe tively, with n = 2
being the ase studied so far [3, 119, 232, 236. Method (i) reformulates the Bethe-Salpeter
equation for the vertex fun tion and has been applied to a two-dimensional, 33 Hubbard
luster. Method (ii) is the method of hoi e for most of the urrent work on vertex orre tions although (a) the expansion of  in terms of W is only asymptoti ally or onditionally
onvergent [237, and (b) Minnhagen [75, 152 nds unphysi al results { i.e., a negative
spe tral density { by extending the GWA approa h for the self-energy of the homogeneous
ele tron gas to se ond order in W . Method (ii) is based on the expe tation that higherorder ontributions to  and P are negligible [3 or are an eled by self- onsisten y e e ts,
whi h is empiri ally supported by the good agreement between standard GWA al ulations
and experiment. In what follows, we dis uss both methods starting with method (i) and,
in addition, dis uss approa hes that in lude vertex orre tions on an LDA level as well as
te hniques that ombine vertex- orre tion and self- onsisten y diagrams.
Iterative solution of Hedin's equations. S hindlmayr and Godby [259 solve Hedin's equations iteratively starting from Hartree theory. The key feature of their approa h is the repla ement of the impli it Bethe-Salpeter equation for the vertex fun tion ( ompare Eq. (21)),
n = order of the iteration)
Z
(n)
(n+1) (1; 2; 3) = (1; 2) (1; 3) +  (1; 2) G(n) (4; 6)G(n) (7; 5) (n+1) (6; 7; 3)d(4; 5; 6; 7)
G(n) (4; 5)
(95)
by an expression whi h depends only on the self-energy of the nth iteration, the vertex
fun tion of the rst iteration, and G(0)
Z
(n)
(n+1) (1; 2; 3) = (1; 2) (1; 3) +  (1; 2) G(0) (4; 6)G(0) (7; 5) (1) (6; 7; 3)d(4; 5; 6; 7): (96)
G(0) (4; 5)
A further advantage of Eq. (96) is that the fun tional derivative (n) =G(0) an in prin iple
be al ulated at all levels of iteration [259. For n = 1 a vertex orre tion (2) is obtained
that ontains not only terms to se ond-order in the RPA s reened intera tion but also terms
of zeroth- and rst-order. Numeri al results for a 33 Hubbard model suggest that an
iterative evaluation of Hedin's equations may improve upon the plasmon satellite spe trum
ompared to standard GWA al ulations.
41

fun tion an be obtained via Dyson's equation [247 (Eq. (16))


G(i! ) = G0 (i! ) + G0 (i! ) [(i! ) + VH Vx  G(i! )

(93)

from whi h the density follows via

2Z0
d! ImG(r; r; ! ):
(94)
 1
Both equations must be solved self- onsistently, sin e a hange in the density yields a hange
in the Hartree potential. Within this approa h [248 Rieger and Godby nd that (i) density
is onserved to within 0.3% in Si and to within 0.05% in Ge, (ii) LDA and GWA stru ture
fa tors di er by less than 0.1% and agree well with experiment, and (iii) a self- onsistent
Hartree potential leads to band stru ture hanges of less than 0.1 eV.

n(r) =

14. VERTEX CORRECTIONS


As follows from Eq. (20), vertex orre tions to the self-energy des ribe the linear response of
the self-energy to a hange in the total ele tri potential of the system. Vertex orre tions in
diele tri s reening des ribe ex hange and orrelation e e ts between an ele tron and other
ele trons in the s reening density. For example, if s reening is provided by a spin-up ele tron
then other spin-up ele trons annot get too lose and are less likely to help with the s reening
[10. As a onsequen e, the s reening is weakened and the intera tion is strengthened. Su h
short-ranged vertex orre tions improve the des ription of quasiparti les and of low-energy
satellites. Other, long-ranged vertex orre tions improve the des ription of the plasmon
satellites as dis ussed in detail in Refs. [14 and [249.
Vertex orre tions in rease orrelation fun tions su h as the density-density response
fun tion, whereas self-energy insertions in the Green fun tion, i.e., self- onsisten y orre tions, redu e orrelation fun tions. DuBois [250, 251 was the rst to noti e that, within
the ontext of the GWA, vertex orre tion diagrams and self-energy diagrams an el ea h
other to a large degree. Due to this an ellation dis repan ies between experiment and
self- onsistent GWA al ulations, su h as those des ribed in the previous se tion, are to be
expe ted. In prin iple, a onsistent treatment of vertex orre tions and self- onsisten y is
required for a quantitative des ription of experiment. Mahan [10, 252 suggests based on the
work of Baym and Kadano [62, 63 and Ward [253 that a onsistent pro edure to in lude
vertex orre tions in the polarizability P an be obtained as follows: The vertex diagrams
asso iated with a self-energy  {  governs the equation of motion of the intera ting Green
fun tion G { that should be in luded in the determination of orrelation fun tions are obtained by atta hing an external intera tion line to the internal Green fun tion lines of the
self-energy diagrams. As a onsequen e, a onsistent onserving approximation for, e.g.,
the in lusion of ladder diagrams in P requires the use of the self- onsistent single-parti le
propagator G rather than the independent-parti le propagator G0 [254. As dis ussed below, most of the self- onsistent or vertex- orre ted al ulations are at varian e with Mahan's
suggestion in one way or another.
40

Hen e, the quasiparti le de ay rate of self- onsistent GWA al ulations shown in Fig. 18 does
not in rease strongly due to the onset of plasmon produ tion { whi h is what is physi ally
expe ted { in ontrast to the G0 W0 A and the GW0 A de ay rates.
Figure 19 shows that the self- onsistent GWA band width of jellium [231 is larger rather
than smaller than the independent-ele tron band width [231, 232, 235. The latter is already
too large in omparison to the experimental band width of simple metals. To explain the
dis repan y between theory and experiment several ombinations of vertex orre tions [184,
232, 240 and the in lusion of surfa e e e ts [229, 241 have been suggested as dis ussed in
the next se tion and Se tion 26 b. A generally a epted explanation for this dis repan y has
not yet emerged.
Total energy al ulations of jellium in the energy- onserving self- onsistent GWA agree
with Monte Carlo data to within 25% (rs = 2) and 1% (rs = 4) [231. S hindlmayr, Pollehn,
and Godby [234 note in this ontext that the total energy of a nite, two-leg Hubbard
ladder is always raised by self- onsistent al ulations relative to standard GWA al ulations.
This is not only true for RPA-based GWA al ulations but also for GWA al ulations that
in lude vertex orre tions and for a Bethe-Goldstone approa h based on the T-matrix [234.
Depending on the approximation used and the parameters of the model the self- onsistent
energy an even be in worse agreement with experiment than the non-self- onsistent energy.
S hindlmayr, Pollehn, and Godby [234 interpret this fa t as an indi ation that the ex ellent
total energies obtained for the ele tron gas with self- onsistent GWA may be fortuitous. The
qualitative hanges in the Hubbard-ladder spe tral fun tion at self- onsisten y (broadening
of high-energy plasmons, sharpening of quasiparti le features) agree with the ndings of
Holm and von Barth [231 and of Eguiluz and S hone [235.
The e e ts of self- onsisten y for real materials are qualitatively similar to those observed
in jellium [230. A self- onsistent GWA al ulation [230 overestimates the valen e-band
width of potassium by more than 1 eV (2.64 eV ompared to 1.60 eV in experiment, 2.21
eV in LDA, and 2.04 eV in standard GWA). Self- onsisten y in reases the quasiparti le
weight by 20% (0.72 ompared to 0.60 non-self- onsistently). Results for Si are equally
dramati [230: the dire t band gap is 4.02 eV in self- onsistent GWA ompared to 3.4 eV
in experiment (2.57 eV in LDA, 3.27 eV in standard GWA) and the indire t band gap is
1.91 eV ompared to 1.17 eV experimentally (0.53 eV in LDA, 1.34 eV in standard GWA).
The self- onsistent o upied band width (13.1 eV) is marginally in better agreement with
experiment [242 (12.50.6 eV) than the result of a standard GWA al ulation (11.65 eV,
11.93 eV in LDA).
Total energy and density. Early total energy al ulations for jellium [243 and bulk Si
[244 based on the Galitskii-Migdal formula [245 have been reported by Levin et al. [243
and Farid et al. [244. In addition, Rieger and Godby [246 re ently determined the density
of Si and Ge in the GWA using the real-spa e/imaginary-time algorithm. In the latter work,
the Hartree potential of Eq. (3) is iterated to self- onsisten y in the presen e of a non-self onsistent GWA self-energy. With G0 as LDA Green fun tion, VH as the hange in the
Hartree potential due to a hange in density, and  as a onstant shift that aligns the Fermi
level of the non-intera ting and intera ting Green fun tions (see above) the intera ting Green
39

(ii) roughly onstant for ondu tion band states with 0  E  25 eV, and (iii) roughly
linearly in reasing for energies E  25 eV. Equation (92) does not apture the behavior of
quasiparti le orre tions over an extended energy range. The overall shape of the energy
dependen e of quasiparti le orre tions in Si is reminis ent of the behavior in jellium [4, 229
and Ag (see Se tion 26 a and Ref. [216).
A truly self- onsistent GWA al ulation not only eliminates the dependen y of results on
the initial starting point of the iteration but is also harge- and energy- onserving in a BaymKadano sense [62, 63. It has the disadvantages that (i) the self- onsistent fundamental
band gap of Si ( 1:9 eV) ex eeds experiment (1.17 eV) by as mu h as LDA ( 0:5 eV) falls
below experiment [230, (ii) the band width of simple metals is larger than independentparti le results and ontradi ts experiment [230, 231, 232, (iii) plasmon-pole peaks in the
spe tral fun tion are strongly suppressed in ontrast to experiment [230, 231, 232, 233, (iv )
the s reened intera tion W does not ful ll the f-sum rule and is only a mathemati al tool to
determine the self-energy, i.e., it has no physi al meaning [231, 232, and (v ) self- onsistent
GWA al ulations are omputationally very demanding. These points will be dis ussed in
more detail below.
The in reasing dis repan y between theory and experiment upon full self- onsisten y
learly indi ates that (i) missing physi s in the form of vertex orre tions must be in luded
in dynami ally s reened intera tion al ulations, and that (ii) in lusion of self- onsisten y
alone is not justi ed due to the in rease in omputational ost and the loss of predi tive
power. The su ess of standard GWA al ulations seems to result from error an ellation
between the la k of vertex orre tions and the omission of self- onsisten y.
Appli ations. Most fully self- onsistent GWA al ulations have been reported for model
systems: a one-dimensional semi ondu ting wire [225, a Hubbard luster [234, and the
homogeneous ele tron gas [231, 235. Self- onsistent al ulations for real solids have been
reported very re ently by S hone and Eguiluz [230. Partially or approximate self- onsistent
al ulations for the same model systems [232, 236, 237 and for the semi ondu tors Si and C
[119 have been reported as well (see below). In parti ular, the al ulations by Shirley [232
and by von Barth and Holm [237 determine the propagator self- onsistently but al ulate
the s reened intera tion from the independent-parti le wave fun tions and energies. We all
this approa h the GW0 A approa h in ontrast to the non-self- onsistent G0 W0 A and the
fully self- onsistent GWA approa h.
Results. Fully self- onsistent GWA al ulations in jellium nd spe tral weight fun tions
whose plasmon satellite weight is signi antly redu ed [231, 235 as shown in Fig. 16. This
trend is in lear ontradi tion to experiments on simple metals whi h show a narrow plasmon
satellite at !pl below the quasiparti le energy and smaller plasmon satellites further down in
energy. Note that the spe tral fun tion of Ref. [235 has dis ernible plasmon peaks rather
than a featureless ba kground as in the spe tral fun tion of Ref. [231. This di eren e may
result from te hni al di eren es in the al ulations ( nite T vs. T=0 approa h, tting of the
spe tral fun tion vs. numeri al evaluation, et .) [238, 239. Loss of plasmon spe tral weight
translates into an in rease in quasiparti le weight as shown in Fig. 17. Also, the broad and
featureless plasmon spe trum of Ref. [231 redu es inelasti quasiparti le-plasmon ollisions.
38

(ii) the s reened intera tion is determined in RPA using the hosen single-parti le wave
fun tions and energies, and (iii) in the majority of ases the frequen y dependen e of the
diele tri response is further approximated by plasmon-pole models. This approa h, whi h
we all the \standard" GWA or G0 W0 A in what follows, works well in pra ti al appli ations
and generally leads to good agreement with experiment for quasiparti le energies. However,
from a prin ipal point of view it has several short omings.
A onsistent approa h to GWA al ulations evaluates the RPA polarizability and the
GWA self-energy using Hartree wave fun tions and energies and iterates the al ulation
until self- onsisten y in G and W is a hieved. Non-self- onsistent results for quasiparti le
energies obtained starting from Hartree theory di er from, for example, LDA-based \best
G, best W " approa hes sin e Hartree wave fun tions and energies are qualitatively di erent
from the orresponding LDA quantities [88. Self- onsisten y eliminates the dependen y of
the nal results on the starting wave fun tions and energies as shown expli itly for a 1D
semi ondu ting wire by de Groot, Bobbert, and van Haeringen [225.
An approximate pro edure for in orporating self- onsisten y into a standard GWA al ulation is to shift the energy spe trum of the independent-parti le Green fun tion su h
that the Fermi levels of the intera ting and the non-intera ting system are aligned [3, 75.
This approximation (i) leads to an in rease of fundamental band gaps by 0.1 to 0.2 eV in
semi ondu tors and insulators [44, (ii) improves the satellite spe trum of a Hubbard luster
signi antly [226, (iii) leads to improved harge onservation in GWA al ulations [227, and
(iv ) is ne essary for systems like NiO to obtain reasonable agreement with experiment [55.
A slightly modi ed version for insulators (see, for instan e, Ref. [46) shifts the independentparti le valen e (v ) and ondu tion ( ) bands in a linear, isotropi manner until they agree
with the orresponding quasiparti le energies

Evk = (1 + Av )"vk + Bv ; E k = (1 + A )" k + B :

(92)

Here Ai and Bi , i = v; , are tting parameters whi h are determined via the band gaps at
two high-symmetry points. Note, however, that Ri e [228 advises against using a shifted
self-energy sin e the energy dependen e of the self-energy is largely an eled by other self onsisten y e e ts. In ontrast to the energies, the independent-parti le wave fun tions are
left un hanged and not repla ed by the intera ting spe tral fun tion. The orresponding
assumption that no signi ant quasiparti le weight is transferred to the satellite spe trum
ontradi ts experiment sin e 10 - 50% of the total spe tral weight resides in the in oherent
ba kground and the plasmon satellites.
Fleszar and Hanke [102 examine the quasiparti le energy shifts in Si as a fun tion of
energy ( 15 eV  E  70 eV) for a non-self- onsistent GWA al ulation that (i) takes
the frequen y dependen e of the s reened intera tion fully into a ount and (ii) a ounts
for nite life-time e e ts, i.e., the nite imaginary part of the self-energy. In most GWA
al ulations point (i) is treated approximately via plasmon-pole models and point (ii) is
negle ted. Figure 15 (right panel) shows that the negle t of the imaginary part of the selfenergy is only justi ed in the immediate vi inity of the band gap. As an be seen in Fig. 15
(left panel), quasiparti le energy shifts are [102 (i) linearly de reasing for o upied states,
37

The lo alized semi ore d states strongly overlap with the wave fun tions of the sameshell s and p ele trons whi h leads to large ex hange energies between the orresponding
states [52. Treatment of the s, p, and d ele trons as valen e ele trons hanges the non-self onsistent self-energy operator qualitatively [52 in that (i) quasiparti le energy orre tions
lower the semi ore d states and lead to improved agreement with experiment, (ii) the selfenergy be omes diagonal in the LDA basis, and (iii) in the ase of CdS, the ex hange between
4s and 5s ele trons in reases the band gap by 0.85 eV. The energy of the semi ore 4d level is
un hanged (E4d = 7:4 eV) regardless of whether 4d, 4d and 4p, or 4d, 4p, and 4s ele trons
are treated as valen e ele trons [52. This suggests that hybridization between ation d
and anion p orbitals is not a e ted signi antly by the s and p ore ele trons. Remaining
self-intera tion errors in the wave fun tion may ause errors in the non-self- onsistent GWA
al ulations on the order of about an eV.
As shown earlier, nonlo al ex hange and in lusion of s reening e e ts due to shallow ore
states are important and a e t quasiparti le properties [43, 197, 198. Ex hange an have
qualitative e e ts on the energy dependen e of the self-energy as demonstrated by Hors h,
von der Linden, and Lukas [216 and dis ussed in Se tion 26 a. Moreover, the results of
Ref. [52 learly illustrate the qualitative importan e of ex hange for the determination of
band stru tures. The quantitative a ura y of the results in Ref. [52 is less ertain, however,
due to te hni al di ulties that are detailed in Se tion 15 a.
Approximate self- onsistent GWA al ulations improve the position of the d bands in
omparison to experiment [213 although (i) the dis repan y between theory and experiment for energy gaps is in reased upon self- onsisten y, i.e., the improvement of quasiparti le energies is not uniform, (ii) vertex orre tions have not been in luded although they
may be important, and (iii) self- onsisten y in reases dis repan y with experiment for all
other known al ulations (see next se tion) with the ex eption of total energies and harge
onservation. The most drasti example of point (i) is CdS [213: the 4d level equals 7.2
eV in LDA [217, 9.1 eV in a partially self- onsistent GWA al ulation, and 9.2/ 9.5
eV in experiment as shown in Table 11. The orresponding values for the band gap are
2.45 eV, 3.21 eV, and 2.50/2.55 eV. Partial self- onsisten y leads to an overestimation of
the dire t band gap by about 0.7 eV. Vertex orre tions (point (ii)) in rease al ulated RPA
ore polarizabilities by about 30% [67 and may be important for semi ore levels as well.
Semi ore states in ZnSe, GaAs, and Ge have been determined within standard GWA by
Aryasetiawan and Gunnarsson [145. As summarized in Table 11, standard GWA al ulations des ribe semi ore levels within 5-15%. The remaining dis repan ies with experiment
are partially due to the la k of self- onsisten y, vertex orre tions, and self-intera tion errors
in the LDA wave fun tions.
13. SELF-CONSISTENCY
General remarks. Most urrent GWA al ulations have three hara teristi s: (i) the Green
fun tion is al ulated in an appropriate single-parti le basis following the \best G, best W "
philosophy (Hartree-Fo k, LDA, or in some ases empiri al pseudopotentials [122, 123, 224),

36

, rl , and re e . Shirley et al. [43 use the experimental ore polarizability [207 and vary
the rl (l = 0; 1; 2) to obtain the orre t removal energy for one valen e ele tron of angular
momentum l outside the ion ore (rl = r2 for l  3) and re e = 0:5(r0 + r1 ).
The two-ele tron potential V^e e is an e e tive intera tion between two valen e ele trons
due to ore-polarization e e ts. This term s reens the bare Coulomb intera tion, whi h
s reening has to be taken into a ount in quasiparti le al ulations. The e e tive intera tion
between valen e ele trons an be expressed as [4, 43
WC = v + v

J v + v

J v

J 6=J

J v + :::
0

(91)

where fJ g are the self- onsistent density-response fun tions of isolated ores [43. The
e e tive intera tion WC repla es the bare Coulomb intera tion in the determination of the
valen e-valen e self-energy in the GWA and in the plasmon-pole sum rules [43.
Shirley et al. [43 use this modi ed GWA approa h and evaluate the self-energy orre tions using LDA wave fun tions and energies. Self- onsisten y in the quasiparti le energies is
a hieved and ore relaxation e e ts are added a posteriori by omparison of LDA all-ele tron
and pseudopotential al ulations.
Core-polarization-potential al ulations give a urate quasiparti le energies for materials
with semi ore states that do not energeti ally overlap with the valen e bands and, in parti ular, des ribe Ge orre tly as an indire t rather than a dire t semi ondu tor [43. Table 10
shows that for Ge and GaAs, the fundamental band gaps are signi antly improved ompared to GWA al ulations that treat ore-valen e intera tions on an LDA level [210.
b. Expli it treatment of ore ele trons
Lo al-orbital basis fun tions [15 su h as Gaussian orbitals [52, 140, 141, 213, 214 or LMTO
[145, 215 allow the expli it treatment of ore ele trons on the same level of approximation as
the valen e ele trons and in lude (i) relaxation and hybridization e e ts on the LDA level,
and (ii) ex hange and dynami s reening e e ts of ore and semi ore ele trons on the GWA
level. The advantage of lo al-orbital basis fun tions ompared to plane-wave methods is the
drasti ally redu ed number of basis fun tions.
In luding semi ore d states as valen e ele trons in non-self- onsistent GWA al ulations
for II-VI materials leads to disappointing results [51, 52: (i) the LDA d levels are shifted
upwards in energy, i.e., away from experiment, and (ii) the self-energy operator is nondiagonal in the basis of LDA states. Unphysi al self-intera tions in LDA { i.e., in omplete
an ellations between Hartree and ex hange potentials { shift the d bands up in energy and
lead to a too strong hybridization with the anion p bands. As a onsequen e of the unphysi al
p-d mixing, the LDA states are not good approximations to quasiparti le states and the
self-energy is non-diagonal. An iterative determination of quasiparti le wave fun tions and
energies in prin iple eliminates the self-intera tion error ontained in the wave fun tions and
energies. However, self- onsisten y alone is not su ient sin e the ex hange intera tion with
the 4s and 4p ele trons must be taken into a ount as well [52.
35

polarization of the ion ores by the valen e ele trons and an be taken into a ount in the
valen e-ele tron Hamiltonian by adding the energy ontribution of all indu ed ore dipoles
in the ele tri eld of the valen e ele trons and of the ore dipoles ex luding self-intera tion
[202, 203. Core polarization fun tions are approximated by stati , atomi polarizabilities
J (J = J th ore at lo ation RJ ) [201, 202. One obtains in a point dipole pi ture [201
X
J 2
VCP P =
EJ ;
(86)
J 2
where EJ is the ele tri eld at RJ
EJ

J 6=J

ZJ

RJ 0

jRJ

RJ
RJ

3+

ri

RJ
RJ 3

jri

(87)

and ri is the lo ation of the ith valen e ele tron and ZJ the atomi number of the J th ore.
The modi ation of the original valen e Hamiltonian VCP P an now be written as [201
8
2

>
X < X
X
R
R
(R
RJ )  (ri RJ )
J
J
J
Z
ZJ J
VCP P =
2
J


3
>
jRJ RJ j J 6=J;i jRJ RJ j3jri RJ j3
J 2 : J 6=J
0

jri

J
2

+2
RJ j4

(ri

9
=


jj

RJ ) (ri0 RJ )
RJ 3 ri0 RJ 3 ;

i<i ri
V^I(J I) + V^e(JI) + V^e(J )
0

+ V^e(Je) :
o

(88)

Besides the standard =(2r4 ) term (V^e , see below), the ele tri elds due to the ions
and valen e ele trons introdu e (i) an additional term V^I I in the ion-ion intera tion of the
total energy of the system, (ii) an additional lo al potential V^e I whi h is felt by every
ele tron, and (iii) an additional intera tion V^e e between two valen e ele trons due to orepolarization e e ts [201, 202, 203. The rst two e e ts are easy to in orporate into standard
band stru ture al ulations. The ontributions due to the valen e ele trons need further
modi ations sin e valen e ele trons annot be des ribed as point harges. For instan e, the
single-ele tron potential V^e for one valen e ele tron far away from a ore of polarizability
redu es orre tly to the lassi al result =(2r4 ) [206. However, valen e ele trons an
penetrate the ore where the lassi al result diverges. A ordingly, a ut-o fun tion has to
be introdu ed [67, 202 and a typi al hoi e is
P
(J )
2
X
J l f (jri RJ j=rl )P^l
;
f (x)  (1 exp( x2 ))2 ;
(89)
V^e =
4
2
j
r
R
j
i
J
J;i
X X
(r RJ )  (ri RJ )
J
f (jri RJ j=re e)f (jri RJ j=re e) i
V^e e =
jri RJ j3jri RJ j3 : (90)
j 2 i6=i
The sum over l in the above equations is a sum over angular momenta and P^l is the orresponding proje tion operator. For ea h atomi spe ies one has to determine the parameters
0

34

agreement with experiment for the stru tural properties of II-VI [188, 189, 190, 191 and of
some III-V (GaAs, GaN, Refs. [192, 193, 194) materials. In general, the equilibrium latti e
parameters are in reased and ohesive energies redu ed. Density distributions are hanged
to su h a degree that bond and interfa e dipoles an hange sign [195, 196. In general,
semi ore states should not be treated via a frozen- ore or a pseudopotential approa h.
Semi ore states also signi antly a e t the ele troni and opti al properties of solids,
sin e, for example, (i) band gaps de rease upon in lusion of semi ore states as valen e
states by about 0.5 eV [191, 192, (ii) the al ulated diele tri onstant in reases by 10-50%
upon in lusion of semi ore states [197, 198, 199, and (iii) for higher-order opti al response
fun tions su h as the oe ient of se ond-harmoni generation in lusion of semi ore states
an give a su iently large e e t that swit hes their sign [195, 200. Sin e quasiparti le
al ulations depend ru ially on an a urate des ription of s reening, a areful treatment of
ore states is ne essary in II-VI semi ondu tors, some III-V materials, alkali metals, alkali
earths, and noble metals.
The LDA des ription of ex hange and orrelation between valen e, semi ore, and sameshell ore ele trons (e.g., Cd 5s, Cd 4d, and Cd 4p, 4s, Ref. [52) is based on a lo al,
energy-independent fun tional of the total density of the system. However, ex hange and
orrelation e e ts between ore and valen e ele trons are non-lo al and energy-dependent.
Dynami orrelation e e ts o ur when u tuating ore dipoles intera t with u tuating valen e densities. These orrelations modify the e e tive intera tion between valen e ele trons.
Rather than intera ting via the bare Coulomb potential v , valen e ele trons experien e an
intera tion potential WC = "C 1 v where "C 1 des ribes the s reening by ore dipoles [201.
The errors due to the LDA an either be eliminated using a ore-polarization-potential
(CPP) approa h [201, 202, 203 { whi h is omputationally e ient, sin e ore ele trons an
still be treated on a frozen- ore or pseudopotential level { or by treatment of ore ele trons as
valen e ele trons [52, 68, 145. The most important error introdu ed by the pseudopotential
approximation is the total negle t of ore relaxation, i.e., of hanges in the ore orbitals due
to a hange in the hemi al environment (e.g., rystal eld e e ts) and to hybridization of
ore and valen e orbitals. These e e ts must be estimated in the CPP approa h whereas
they are in luded on an LDA level when ore ele trons are treated expli itly. Also, the
semi ore d states of II-VI materials energeti ally overlap the valen e band and hen e annot
be eliminated via a ore-polarization potential. Expli it in lusion of the d ele trons in the
valen e band amounts to a signi ant in rease in omputational ost for plane-wave-based
quasiparti le al ulations [204 su h as the one used in Ref. [43. Other approa hes that
des ribe semi ore states via only nonlinear ore orre tions [205 have been shown to give
band stru tures in good agreement with experiment for II-VI materials [51. However, this
agreement must be onsidered oin idental, sin e it relies upon error an ellation between
ore relaxation and ore-valen e ex hange and polarization e e ts.
a. Core-polarization potentials
Dynami al intershell orrelation between semi ore and valen e ele trons leads to indu ed
33

Besides band-gap redu tion, the energy dependen e of  is important in hanging the
dispersion of bands whi h follows from the omparison of the expe tation value h(E ) Vx i
with the expe tation value evaluated at the mid-gap energy h(0) Vx i [185. For Si,
Fig. 12 panels a) - ) show [185 (i) the expe tation value h(E )i has a pronoun ed state
dependen e, whi h is largely an eled by subtra ting the expe tation value of the ex hange orrelation potential, (ii) h(E ) Vx LDA i is dominated by a jump at the energy gap and a
at dispersion for both o upied and uno upied states, (iii) h(0) Vx LDA i shows a larger
jump at the band gap than h(E ) Vx LDA i and a linear dispersion for both o upied and
uno upied states, and (iv ) with the ex eption of the jump at the Fermi energy the energy
dependen e an be modeled by the energy dependen e of the jellium self-energy. Hen e, the
e e t of the energy dependen e of the self-energy, besides the redu tion in the band gap, is
a signi ant hange { from linear to at { in the dispersion of the bands.
Self-energy orre tions in small- and medium-gap semi ondu tors align the theoreti al
and experimental band gaps by an approximately rigid shift, the so- alled s issors shift.
Although the s issors-shift approa h works well in Si, it breaks down in wide-band-gap
materials su h as SiC and GaN, as shown in Fig. 14. The in reased dispersion in the selfenergy orre tion for SiC and GaN may indi ate that the LDA wave fun tions are less and
less good approximations to the quasiparti le wave fun tions as the band gap in reases. A
review of appli ations of and extensions to the s issors-shift approa h for the determination of
opti al response fun tions is given in Se tion 30. A related observation is that the deviation
of the highest o upied eigenvalue in LDA from the highest o upied DFT eigenvalue, whi h
equals the highest o upied quasiparti le eigenvalue (see Se tion 3), in reases with in reasing
ioni ity of the material under onsideration [44. This deviation amounts to about 0.1 eV
for ovalent semi ondu tors su h as Si and Ge. For more ioni materials su h as diamond
and LiCl, the deviation is as large as 1.5 eV.
A simpli ed model of the self-energy of an insulator approximates its non-lo ality and
energy dependen e by the orresponding quantities of the jellium self-energy evaluated at
the lo al density in the insulator [185. Figure 12, panel e) shows that the variation of the
self-energy with respe t to energy an be modeled by results obtained from the homogeneous
ele tron gas. Assuming that the energy dependen e of the self-energy fa tors out ompletely
and onsidering the observations in the previous se tion, Godby, S hluter, and Sham [185
suggest the following physi ally appealing approximation for the self-energy:
1
(85)
(r; r0 ; E )  [f (r) + f (r0 )g (jr r0 j)h(E );
2
where g (jr r0 j) and h(E ) are fun tions that des ribe the non-lo ality and energy dependen e
of the self-energy of jellium. The fa tor (f (r)+ f (r0))=2 a ounts for lo al- eld e e ts. To the
best of our knowledge appli ations of this formula have been limited to model al ulations.
12. CORE-POLARIZATION EFFECTS
A ounting for the hybridization of valen e orbitals with semi ore orbitals [187 and the
relaxation of the latter (e.g., d orbitals in II-VI materials) in al ulations leads to better
32

hole of the self-energy mirrors the non-lo ality of the short-ranged s reened intera tion W
rather than the long-ranged single-parti le propagator G. The average radius of the rst
nodal surfa e of the non-lo ality in jellium is 2rs (2.1 
A for Si). The extent of the nonlo ality is on the s ale of a typi al wavelength of a ondu tion-band wave fun tion and the
hole a ounts for more than 99% of the self-energy expe tation value in Si. The non-lo ality
of the self-energy ontributes signi antly to the step-like stru ture in the self-energy orre tions at the band gap shown in Fig. 12, panels a) and b) for Si [185. Panel ) of the same
gure shows that this step-like stru ture is absent in jellium whi h indi ates that although
the overall form (not the depth) of the non-lo ality hole is well reprodu ed by jellium at the
appropriate density, the intera tion between the wave fun tions and the non-lo ality is not
aptured in the homogeneous ele tron gas [185.
Evaluation of the self-energy operator of jellium at the lo al density of Si leads to an
underestimation of the self-energy non-lo ality radius by about 30% in the bonding region
and an overestimation by about 80% in the interstitial region as shown in Table 8. This
result questions the validity of basi assumptions in the QPLDA [185. In addition, the nonlo ality hole is too anisotropi , and it therefore seems unlikely that QPLDA (see Se tion 9 d)
an give quasiparti le energies of an a ura y omparable to the full GWA results.
11. ENERGY DEPENDENCE OF THE SELF-ENERGY
Table 6 shows that the dynami ally s reened intera tion approximation redu es the 0.8
to 2.2 eV overestimation of dire t band gaps in the stati COHSEX approximation to a
dis repan y of 0.1 to 0.3 eV between theory and experiment [44. A quantitative predi tion
of quasiparti le energies requires a orre t treatment of the energy dependen e of the selfenergy. A simple interpretation of the dynami al e e ts an be obtained by realizing that
the ele tron drags a polarization loud behind it. S reening and the asso iated s reening
energy will depend on the velo ity of the ele tron. The strongest s reening and therefore
the lowest energy is obtained in the stati ase. In luding energy dependen e will lead to a
s reening energy that is not as low and hen e remedies the overestimation of the self-energy
in the COHSEX approximation.
The band-gap redu tion results from the linear behavior of the self-energy as a fun tion
of energy lose to the quasiparti le energy. Figure 13 shows that the expe tation values of
the self-energy operator in diamond, Si, Ge, and LiCl have a negative slope of about 0:2
[44. This slope translates into nearly onstant quasiparti le weights Zi of about 0.8, as
shown in Table 9 (Eq. (18)), and to an about 20% redu tion in the quasiparti le shifts via
Eq. (17). However, the quasiparti le weights Zi are lose enough to unity, that quasiparti les
are well de ned ex itations for energies lose to the band gap although dynami al e e ts are
non-negligible. This statement is no longer valid in d and f ele tron systems as dis ussed
in Se tion 26 . The urves of (E ) bend upwards for hole and downwards for ele tron
states whi h agrees with al ulations of the energy dependen e of the self-energy of jellium
[4. Core ele trons an qualitatively hange the energy dependen e of the self-energy, as
dis ussed for the ase of Ag in Se tion 26 a.
31

where the ex hange density nx is de ned as

nx (r; r0 ) =

i (r)i (r0 ):

(84)

Negle t of lo al elds leads to homogeneous s reening, W s r (r; r) is onstant and does not
ontribute to dispersion within a band gap or a given band. Based on the above remarks
about the strength of W s r in bonding and antibonding regions one expe ts (i) an in rease
in the fundamental gap due to COH upon in lusion of lo al- eld e e ts, and (ii) a strong
lo al- eld e e t on the expe tation value of COH for o upied but not for uno upied states.
Both expe tations are on rmed by a tual al ulations as shown in Tables 6 and 7.
Lo al- eld e e ts are somewhat weaker for the s reened-ex hange ontribution to the
self-energy sin e SEX is dominated by the bare Coulomb intera tion when jr r0 j is less
than a typi al bond length, i.e., within the range of the lo al- eld e e ts. Table 7 shows,
that for o upied states lo al- eld e e ts in SEX amount to about a third of the lo al- eld
e e ts in COH and that lo al- eld e e ts for uno upied bands in SEX are even smaller.
Sin e lo al- eld e e ts in SEX and COH are of opposite sign and amount at least to
several tenths of an eV, they must be in luded in the determination of both terms to ensure
quantitatively a urate results. The strong e e t of lo al elds on COH for the valen e band
with respe t to the ondu tion band and the relative insensitivity of SEX to lo al elds
leads to a band gap in rease of 0.8 to 4.4 eV ompared to the LDA or the stati COHSEX
approximation without lo al elds.
Table 6 demonstrates that [44 (i) LDA gives band gaps that are at least 0.5 to 2.0 eV
smaller than experiment (see also Fig. 3), (ii) the COHSEX approximation without lo al
elds gives band gaps that are in better agreement with experiment although signi ant deviations from experiment remain, and (iii) lo al elds dramati ally open up the band gap and
require in lusion of dynami s reening to a hieve quantitative agreement with experiment.
Lo al- eld e e ts on the self-energy shifts in simple metals are less than the numeri al
un ertainties of GWA al ulations (see Se tion 26 b and Ref. [184) sin e their density is
relatively homogeneous ompared to ovalently-bonded semi ondu tors.
b. Nonlo ality of the self-energy
The s reened-ex hange ontribution to the self-energy is proportional to the non-lo al ex hange density (Eq. (83)) and hen e sensitive to the nodal stru ture of wave fun tions, whi h
results in a dis ontinuity of the expe tation value of SEX upon rossing the band gap [185.
This dis ontinuity, dis ussed in onne tion with Fig. 9 and Table 7, shows a 0.3 eV sensitivity to the in lusion of lo al- eld e e ts [186. The Coulomb-hole self-energy (Eq. (82)) does
not experien e any non-lo al e e ts upon rossing the band gap sin e it is a lo al operator.
Figure 11 shows that the non-lo ality of the self-energy (r; r0 ; E ) of ommon semi ondu tors in real spa e is dominated by a spheri al hole entered around r = r0 whose shape
{ but not its strength or depth { is roughly independent of the lo ation of r and an be
approximated by the orresponding hole of the jellium self-energy [185. The non-lo ality
30

whose diagonal matrix elements a ount for homogeneous s reening (see Se tion 31 for a
detailed dis ussion). Lo al- eld e e ts are often important in semi ondu tors and insulators
but rarely in metals.
In ontrast to lo al operators { whi h depend only on one real spa e variable r and a t
multipli atively on a wave fun tion { non-lo al operators su h as the self-energy depend on
two independent real-spa e variables and a t on wave fun tions via a nontrivial real spa e
integral, i.e., they probe the wave fun tion Rnot only for r = r0 but for all r0 within their
range. Figure 9 shows s hemati ally that (r; r0 ; E )(r0 )dr0 will be large and negative
for the highest valen e band wave fun tion v and mu h smaller in absolute value for the
lowest ondu tion band wave fun tion  of Si. The extra node of the ondu tion band wave
fun tion leads to an eling positive and negative ontributions to the integral and ontributes
to the dis ontinuous jump of self-energy orre tions at the band gap (see below).
The ombined e e t of lo al elds and the non-lo ality of the self-energy operator on
the band gap of solids is signi ant and annot learly be separated into two distin t ontributions. For instan e, lo al- eld e e ts modify the range of the self-energy. Despite the
interdependen e of lo al- eld e e ts and the self-energy non-lo ality, the next two paragraphs
dis uss the dominant in uen e of lo al elds and of nonlo ality on self-energy orre tions
separately.
a. Lo al elds
A real-spa e analysis of the stati s reening potential W s r (r; r0) = W (r; r0; E = 0) v (r; r0)
around an extra ele tron entered at a bond enter or at an interstitial site [44 shows that
(i) lo al elds ontribute to more than a third of the s reening potential in the region near
the enter of the bond, (ii) the lo al- eld ontribution is mu h smaller (roughly one tenth)
in the low-density, interstitial regions, (iii) lo al elds are responsible for the anisotropy of
the s reening potential, and (iv ) lo al elds are short-ranged and their e e t is negligible
beyond roughly one bond length. Figure 10 shows the results for W s r evaluated at E = 0
in analogy to the stati COHSEX approximation to separate the energy-dependen e of 
from lo al- eld e e ts.
The s reening potential due to an ele tron at site r evaluated at the same site determines
the Coulomb-hole ontribution to the self-energy whi h onsequently is (i) onstant when
lo al elds are negle ted, and (ii) mu h deeper in the bonding region than in the interstitial
region when lo al- eld e e ts are taken into a ount. Lo al elds are more important for
valen e than ondu tion bands sin e the valen e band density is on entrated in the bonding region and the ondu tion band density is on entrated in the interstitial region. The
Coulomb-hole and s reened-ex hange ontributions to the self-energy an be expressed in
terms of the s reening potential W s r as follows (see Eqs. (43) and (44))
1
COH (r; r0) = (r r0 )W s r (r; r);
(82)
2
#
"
1
1
SEX (r; r0) =
(83)
nx (r; r0 ) W s r (r; r0 ) +
2
jr r0j ;
29

s ale as the number of basis fun tions to the fth power [179 ompared to standard LDA
and GWA al ulations that s ale as the number of basis fun tions to the third and fourth
power, respe tively. Appli ations of proje tor methods to ex ited-state properties have been
reported for Si, Egap = 3:0 eV (3.3-3.4 eV experiment); diamond, Egap = 7:2 eV (7.3 eV
experiment); and Ge, Egap = 0:44 eV (0.9 eV experiment).
d. Quasiparti le lo al density approximation (QPLDA)
The self-energy is a short-ranged operator [39 and { as a ground-state property { a fun tional of the ground state density [39. For systems with slowly varying density, a possible
approximation of  is given by the self-energy h of the homogeneous ele tron gas evaluated
at the lo al density [39:
(r; r0 ; E )  h (p(r); E

 h (n(r)); n(r)) (r

r0 ):

(81)

Here p(r) is a lo al momentum and the hemi al potentials of the inhomogeneous () and
the homogeneous (h) system are introdu ed to line up the Fermi levels. Cal ulations on
metals using this approximation are, for instan e, reported by Arbman and von Barth [86
for Al and by Sa hetti [180 for Cu.
For pra ti al al ulations [160, 161, 162, 181 in semi ondu tors the homogeneous selfenergy is evaluated in the GWA with the further assumptions that (i) the Levine-Louie
diele tri fun tion des ribes s reening, and (ii) the Green fun tion equals the Green fun tion
of a titious, insulating, free ele tron gas. Although this ansatz is guided by physi al
intuition, it la ks rigorous justi ation [86, 160 and may elude systemati improvements
[160. Advantages of the QPLDA are (i) it is not limited to minimal basis sets in ontrast
to the early work of Hanke et al. [154, 155, 156 and Fulde et al. [157, 158, 159, and (ii)
it leads only to a 30% in rease in omputation time ompared to LDA and is therefore very
e ient ompared to the other methods dis ussed above.
Important physi s of the many-body self-energy is not aptured in QPLDA sin e (i) the
energy-dependen e of the QPLDA self-energy in reases the LDA band gaps and a hieves satisfa tory agreement with experiment, and (ii) lo al- eld e e ts are not taken into a ount.
In more a urate GWA al ulations stati , inhomogeneous s reening e e ts open the LDA
band gap of semi ondu tors, and dynami e e ts redu e the gaps to within a few tenths
of an eV of the experimental values (see next se tions). Nevertheless, QPLDA band gaps
generally agree with experiment to within 0.4 eV. For example, the dire t band gap of Si is
2.99 eV ompared to experimental values of 3.3 to 3.4 eV, and the indire t gap equals 0.81
eV ompare to an experimental value of 1.17 eV [162.
10. LOCAL-FIELD EFFECTS AND THE NONLOCALITY OF THE SELF-ENERGY
The response of an inhomogeneous density distribution to an external ele tri eld gives rise
to mi ros opi elds that vary on the length s ale of a bond length. These so- alled lo al
elds are des ribed by the o -diagonal matrix elements of the diele tri matrix (Eq. (26))
28

where ontributions due to W=G are negle ted sin e they are di ult to handle, and in
addition their ontributions are estimated to be negligible for Si and diamond [169. Using
the above expression for the vertex fun tion in the de nition of the polarizability as well as
the diele tri matrix, one nds that the diele tri matrix in ludes not only RPA bubbles,
orresponding to (1; 2) (1; 3) in the above equation, but also an in nite series of s reened
ladder diagrams resulting from the se ond term in Eq. (79). Note that Mahan [10 uses
Ward identities to justify the simultaneous in lusion of identi al vertex orre tions in  and
P in ontrast to the approa h suggested by Hanke et al. Mahan's approa h is dis ussed in
more detail in Se tion 14.
In lusion of ex itoni e e ts via the solution of the Bethe-Salpeter equation for several
semi ondu tors leads to [156, 169, 170, 171, 172: (i) band gaps and valen e band widths in
good agreement with experiment, (ii) an in rease in os illator strength at the E1 peak of the
frequen y spe trum of " by 50-100% in good agreement with experiment, and (iii) a larger
E1 peak intensity than E2 peak intensity for Si in ontrast with experiment (see Fig. 39
for a de nition of the E1 and E2 peaks in the imaginary part of the Si diele tri fun tion).
Pra ti al al ulations use a matrix representation of the Bethe-Salpeter equation with respe t to semi-empiri al tight-binding valen e and ondu tion bands, whi h are expressed in
a Gaussian-orbital basis set [156, 169.
. Lo al approa h
Lo al approa hes to the orrelation problem in solids (for a review see Ref. [19) are based on
the physi al pi ture that adding an ele tron or hole to an insulator leads to a polarization of
neighboring bonds whose indu ed dipoles will a t on and hange the energy of the original
parti le. A lo al des ription of orrelation e e ts based on quantum hemistry methods
starts from a Hartree-Fo k wave fun tion and in ludes lo al orrelations in the form of
one- and two-parti le [173 ex itations in the many-body wave fun tion j i via a proje tion
operator exp(S^)
j i = exp(S^)j HF i:
(80)
The operator S^ depends on parameters that hara terize ground- and ex ited-state orrelations and that an be determined variationally.
Bond polarizations are interatomi orrelation e e ts that dominate diele tri s reening
and hen e quasiparti le energy shifts of o upied and uno upied states in ovalent semi ondu tors. These interatomi orrelation e e ts an be des ribed by proje tor methods whi h
are based on a minimal basis set of Gaussian orbitals [157, 158, 159. Other important effe ts like the relaxation of ele troni orbitals in the neighborhood of an added ele tron or the
hange of ground-state orrelations due to the presen e of an extra ele tron require a larger
basis set. Ea h of these two, partially an eling e e ts is estimated to amount to band gap
orre tions on the order of 1-2 eV based on mole ular al ulations [157, 158, 159.
Lo al proje tor methods determine ground-state properties of a variety of semi ondu tors
with better a ura y than LDA [174, 175, 176, but appli ations to ex ited states are limited
and remain di ult due to the extended nature of these states [177, 178. The al ulations
27

in whi h photons reate intera ting ele tron-hole pairs { than RPA-based approa hes. In
ontrast to RPA-based GWA al ulations whose fundamental ex itations are non-intera ting
ele tron-hole pairs and plasmons, GWA al ulations based on a des ription of s reening in the
time-dependent Hartree-Fo k approximation in lude the short-range, attra tive intera tion
between ele trons and holes via ladder diagrams.
The determination of the in uen e of ex itoni orrelations on density u tuations and
hen e on the diele tri matrix requires the solution of the equation of motion of the twoparti le Green fun tion, i.e., the Bethe-Salpeter equation [154, 155, 156. The inverse diele tri matrix is given in terms of the density-density orrelation fun tion [165 and the latter
an be written as a two-parti le Green fun tion [167
hN; 0jT [^n(rt)^n(r00)jN; 0i = iG(rt; r00; r00+; rt+):
(75)
0
0
0
Let G (1; 1 ; 2; 2 ) be the non-intera ting ele tron-hole propagator
G0 (1; 10; 2; 20) = G(10 ; 20 )G(2; 1);
(76)
and I the irredu ible ele tron-hole intera tion whose approximation is shown in Fig. 8 [168
I (3; 30 ; 4; 40) = (3; 4) (30 ; 40)Wx (3; 30) + (3; 30 ) (4; 40)v (3; 4):
(77)
Here Wx is a stati approximation to the s reened intera tion between an ele tron and a
hole and v is the uns reened Coulomb repulsion. Choosing Wx = 0 leads ba k to the RPA
results. Solution of the Bethe-Salpeter equation
Z
G(1; 10; 2; 20 ) = G0 (1; 10 ; 2; 20) + G0 (1; 10; 3; 30 )I (3; 30; 4; 40)G(4; 40 ; 2; 20)d(3; 30; 4; 40) (78)
determines of the in uen e of ex itoni orrelations on the frequen y dependen e of the
diele tri matrix (via Eqs. (75) and (29)) and on the quasiparti le spe trum (via Eqs. (3)
and (22)).
The in lusion of vertex orre tions in the irredu ible polarizability but not in the selfenergy is motivated by two observations: (i) An exa t Ward-identity-based relation between the self-energy and the vertex fun tion is expe ted to be better observed when the
irredu ible polarizability is determined in the time-dependent Hartree-Fo k rather than the
time-dependent Hartree approximation [156. This Ward-identity-based relation results from
harge onservation. (ii) Hanke and ollaborators suggest that the evaluation of the GWA
self-energy with an intera tion s reened using the time-dependent Hartree-Fo k approximation is more appropriate than an evaluation of  using an RPA-s reened intera tion. The
hoi e of s reening in the time-dependent Hartree-Fo k approximation an be motivated as
follows: Choosing  = 0 in Fig. 4 as the starting point for an iterative solution leads to
(1; 2; 3) = (1; 2) (1; 3) and " = "RP A (see Eqs. (21) and (34)). The next iteration yields
(1; 2) = iG(1; 2)W (1+; 2) and subsequently
Z
[iG(1; 2)W (1+; 2)
(1; 2; 3) = (1; 2) (1; 3) +
G(4; 6)G(7; 5) (6; 7; 3)d(4; 5; 6; 7)
G(4; 5)
Z
= (1; 2) (1; 3) + i W (1+ ; 2)G(1; 6)G(7; 2) (6; 7; 3)d(6; 7);
(79)
26

the GWA extensions ompared to stati COHSEX al ulations are dis ussed in the following
se tions.
Appli ations. Work on bulk insulators was done by Lipari and ollaborators (NaCl, NaBr,
solid Ar; Refs. [133, 134, 135, 136) as well as by Kane (Si; Ref. [137) in the early seventies;
by Brener in the mid-seventies (LiF, diamond; Refs. [138, 139); by Louis in the late seventies
(AX, A = Li+, Na+ , X = F , Cl , Br , I ; Ref. [146); and by Baroni and ollaborators
(solid Ar, LiH; Refs. [140, 141) as well as by Gygi and Balderes hi (Si; Ref. [90) in the
mid-eighties.
Cal ulations on potassium and other metals are, for instan e, reported by Bross and
ollaborators (see Ref. [99 and referen es therein). The starting Hamiltonian for potassium
is de ned by a \parametrized Thomas-Fermi-like" approximation to the stati self-energy
[99, 147:



Z
o
X
exp( jr r0 j)
1 2
r
+ VH + Vext i (r) + i (r) i (r0 )
i (r0 )dr0 = "i i (r): (74)
0
2
jr r j
i
0

Modeling the frequen y dependen e of the s reened intera tion by Lundqvist's plasmon-pole
model [98 (see Se tion 8) and ore-valen e polarization using the dipolar ore polarizability
of potassium leads to quasiparti le energies that agree to within 20% with experiment [99.
The in lusion of ore polarization redu es self-energy shifts by 0.1 to 0.2 eV [99.
Other appli ations of the stati COHSEX approximation in lude Gadzuk's determination of polarization energies of ore holes in atoms or mole ules that are embedded in or
adsorbed on the surfa e of a free ele tron gas (Ref. [148 and referen es therein). Hodges
[149 uses a dynami COHSEX approximation to explore the image potential of a harged
parti le trapped at the surfa e of a metal and Cooper and Linderberg [150 use the COHSEX approximation within the Pariser-Parr-Pople model for the des ription of  -ele tron
systems in hydro arbons. Theoreti al issues, su h as the importan e of vertex orre tions,
have been addressed by several authors [151, 152, 153. We review these works in more detail
in Se tion 14, where we dis uss vertex orre tions to the GWA.
Several alternative or more general approa hes for the determination of quasiparti le
energies have been suggested in the literature. The approa hes by Hanke and ollaborators [154, 155, 156, by Fulde and ollaborators [157, 158, 159, and by Wang and Pi kett
[160, 161, 162 are dis ussed in some detail in the paragraphs below sin e they either extend RPA-based GWA al ulations or orrespond to interesting alternative pi tures for the
des ription of ex hange and orrelation in solids. Other approa hes su h as the ele troni
polaron model by Kunz [163 or by Hermanson [164 an be identi ed as limiting ases of
GWA al ulations [65. Their physi s is ontained in the general dis ussion of the GWA
approa h and we do not dis uss these referen es separately.
b. Ex itoni e e ts
An extension of the COHSEX approximation [154, 155 that in ludes ex itoni orrelations
in the irredu ible polarizability gives a better des ription of photoabsorption experiments {
25

This se tion reviews the history of GWA al ulations and outlines some related approa hes.
As in the se tion on the model diele tri matri es, we on entrate on work done on semi ondu tors and insulators. We fo us our survey on the time span between 1970-1986. Before
1970 most of the GWA work was done on the homogeneous ele tron gas. The only work on
semi ondu tors is the paper by Brinkman and Goodman [83. These papers are thoroughly
reviewed in Refs. [4 and [132. In 1985, rst-prin iples quasiparti le al ulations were done
by Hybertsen and Louie [5 and in 1986 by Godby, S hluter, and Sham [6. First-prin iples
GWA al ulations are dis ussed at length starting in Se tion 10.
a. Stati COHSEX al ulations
General onsiderations. The error an ellation between the negle t of dynami al e e ts in
the stati COHSEX approximation and the negle t of lo al- eld e e ts due to the use of a
diagonal model diele tri fun tion { whi h is the ommon hara teristi of all quasiparti le
al ulations on bulk insulators in the 1970s and early 1980s { results in dire t quasiparti le
band gaps that agree well with experiment as is shown in Table 4. Indire t band gaps,
however, di er signi antly from experimental values. In the ase of sili on [90, the rst
few ondu tion bands at are at 3.24 and 4.41 eV in omparison to experimental values of
3.4 and 4.2 eV. The indire t band gap is 0.68 eV and hen e underestimates the experimental
value of 1.17 eV by about 0.5 eV. As a onsequen e, the stati COHSEX approximation
annot repla e the dynami ally s reened intera tion approximation if one is interested in the
full band stru ture.
Hartree-Fo k al ulations o er a onvenient single-parti le basis for low-polarizability
solids { whi h are the fo us of mu h of the early work in the COHSEX approximation
{ but fail to give a good des ription of polarizable solids su h as Si for whi h empiri al
pseudopotential or LDA wave fun tions and energies work better. Table 5 shows that in
the ase of Si [90, self- onsistent COHSEX and LDA densities are very similar whereas
Hartree-Fo k al ulations on entrate too mu h density in the bonds.
Core-valen e ex hange and orrelation potentials an either be treated via e e tive (e.g.,
ore-polarization) potentials or by treating the ore ele trons on the same level of approximation as the valen e ele trons. Expli it treatment of ore ele trons using a linear- ombinationof-atomi -orbitals basis [138, 139 or a basis set of lo alized, ontra ted Gaussian-type orbitals [140, 141 { whi h allow the analyti evaluation of s reened-ex hange two-ele tron
integrals { has been the method of hoi e in stati COHSEX al ulations. Alternatively, uns reened ore- ore and ore-valen e ex hange potentials from Eq. (46) are taken into a ount
in stati COHSEX al ulations but self-energy ontributions due to ore-valen e polarization
are negle ted [133, 134, 135, 136.
Re ent GWA al ulations [5, 6 extend earlier COHSEX work by using a non-diagonal,
frequen y-dependent [144, rst-prin iples diele tri matrix for the determination of quasiparti le orre tions to the single-parti le spe trum. The treatment of ore ele trons is (i) at
LDA level [5, 6, (ii) impli it via ore-polarization potentials [43, and (iii) expli it by treating ore ele trons on the same level as valen e ele trons [52, 68, 145. The onsequen es of

24

The Engel{Farid plasmon-pole model an be obtained by diagonalizing the above equation,


whi h is equivalent to the solution of the following generalized eigenvalue problem
1
L(q)xpq
2
!p (q)

(q; 0)xpq =

(67)

The eigenve tors xpq are normalized as follows


xypq L(q)xp0 q

= pp :
0

(68)

De ning the s aled eigenve tors ypq as


ypq

= L(q)xpq

(69)

one nds for the spe tral represenation of 

GG (q; ! ) =

and its inverse

ypq(G)ypq(G0 )
! 2 !p2(q)

1 (q; ! ) = X xpq (G)(! 2


GG
0

!p2 (q))xpq (G0 ):

(70)
(71)

These equations de ne the Engel{Farid plasmon-pole model. For future referen e in the
determination of the self-energy using the Engel{Farid plasmon-pole model, we de ne s aled
plasmon-pole eigenve tors as
pq (G) =

4
1
ypq(G):
2!p(q) jq + Gj2

(72)

An interpretation of the plasmon-pole eigenvalues as plasmon energies as suggested by


Engel and Farid leads to an agreement between theory and experiment to within 10% for
plasmon energies !0 (0) and to within 30% for the small q-ve tor dispersion oe ient ,
!0 (q)  !0 (0) + jqj2 , in the ase of the semi ondu tors Si, Ge, GaAs, SiC, and GaN as is
shown in Table 3. Mar h and Tosi [131 show that the plasmon frequen ies of a system are
the zeros of the determinant of the inverse full polarizability  1 :
h
i
det  1 (q; !q ) = 0:
(73)
GG0

This observation in onjun tion with Eq. (71) leads Engel and Farid [120 to interpret the
eigenenergies of Eq. (67) as plasmon energies and their small q-ve tor dispersion oe ient
as plasmon dispersion oe ient.
9. EARLY QUASIPARTICLE CALCULATIONS
23

matrix "~ under the assumption that the energy dependen e of "~ is ontained in its eigenvalues
only. De ne the following symmetrized, Hermitian diele tri matrix

"~GG (q; ! ) =
0

j q + G j " (q; ! );
jq + G0 j GG

(60)

whose inverse "~ 1 has the eigenvalue de omposition [122, 123


X
"~ 1 (q; ! ) = jpq(! )i 1 (! )hpq(! )j:

(61)

pq

where p numbers the real, positive eigenvalues pq1 (! ) and the orresponding eigenve tors
jpq(!)i. Assume that the frequen y dependen e of the inverse diele tri matrix is solely
ontained in the eigenvalues (jpq (! )i = jpq (! = 0)i) and is of the form [122, 123
"

z ! (q)
pq1 (! ) = 1 + pq p
2
!

1
1
;
(62)
(!p(q) i ) ! + (!p (q) i )
where the plasmon pole strength zpq = 1 pq1 (0) is determined by omparison with the
stati diele tri matrix. With the de nition of the s aled plasmon-pole eigenve tors as
pq (G) 

pq (G)
j q + Gj

(63)

and the \ rst-moment" matrix


2 (1)
 (q)
 GG
one an express the plasmon-pole frequen ies using Johnson's sum rule [116 as
! 2 X pq (G)
n (G G0 ) pq (G0 )
!p(q)2 = pl
(q + G)  (q + G0 ) 0
zpq GG jq + Gj
n0 (0) jq + G0 j
4
=
h jL(q)jpqi:
zpq pq

LGG (q)  (q + G)  (q + G0 )n0 (G


0

G0 )

(64)

(65)

Subsequently, the energy integration of Eq. (35) an be done and the result is given in
Se tions 15 and 16 for a plane wave basis.
Engel and Farid. Engel and Farid [120 derive a N -parameter plasmon-pole model whose
eigenvalues and eigenve tors are frequen y dependent by expli itly onstru ting an approximation  to the full polarizability , whi h approximation is exa t in the stati and the
high-frequen y limits. With , , and L 1 , the inverse of the rst-moment matrix L in
Eq. (64), as matri es in the re ipro al latti e ve tors G and G0 the approximation  to the
full polarizability  an be expressed as [120
h
i 1
(q; ! ) = ! 2L 1 (q) +  1 (q; 0) :
(66)
22

the diele tri matrix { via reprodu tion of the rst frequen y moment. As a onsequen e,
energy integrations of the s reened intera tion are su iently a urate for the determination
of quasiparti le energies and e e tive masses [115. The e e tive strength and frequen y of
the plasmon ex itation are determined by for ing the model to reprodu e the stati diele tri
matrix in the zero-frequen y limit and by using Johnson's sum rule [116, 117. The latter
sum rule onne ts the rst frequen y moment of the full polarizability  = n=Vext [120

(1) (r; r0; ! ) =
lim ! 2(r; r0 ; ! );
(58)
2 j!j!1
with the ground state density n0 (G) of the rystal

(q + G)  (q + G0 )n0 (G G0 ):
(59)
(1)
GG (q) =
2
In RPA,  is related to the irredu ible polarizability P = P 0 in matrix notation via (q; ! ) =
P (q; ! )[1 v (q)P (q; ! ) 1.
Quasiparti le energies in jellium al ulated with the RPA diele tri fun tion or with the
Lundqvist plasmon pole model [98, 100, 101 are very lose (see previous Se tion) whi h
indi ates that the negle t of ele tron-hole ex itations in plasmon-pole models is justi ed for
energies lose to the Fermi energy. Similar observations hold for semi ondu tors as dis ussed
above.
The plasmon-pole assumption that the only possible quasiparti le de ay me hanism {
des ribed by the imaginary part of the diele tri matrix { is due to quasiparti le s attering
o plasmon ex itations results in nite quasiparti le life times only at plasmon frequen ies.
Plasmon-pole models fail to give good des riptions of systems whose imaginary self-energy is
large [115. In parti ular, low-lying valen e states and hen e the valen e band width are not
des ribed a urately. For example, Table 21 shows that taking the full frequen y dependen e
of the diele tri matrix into a ount leads to a valen e-band narrowing of about 0.3 eV in
Si ompared to a plasmon-pole model al ulation ( ompare the frequen y-dependent results
of Refs. [102, 103 with results using plasmon-pole approximations su h as Ref. [42, see also
Ref. [89).
Hybertsen and Louie [44 approximate ea h matrix element of the diele tri matrix by
a plasmon-pole model whi h results in (i) N 2 plasmon-pole parameters (N = size of the
diele tri matrix), (ii) a non-trivial extension of the model to systems without inversion
symmetry [121, and (iii) unphysi al solutions with imaginary plasmon-pole energies for some
o -diagonal matrix elements. Rather than on entrating on the details of the HybertsenLouie plasmon-pole model, we onsider two alternative plasmon-pole models suggested by
von der Linden and Hors h [122 and Engel and Farid [120. Both models give identi al
expressions for the expe tation value of the self-energy operator provided that appropriately
s aled plasmon-pole eigenvalues and eigenve tors are introdu ed (see below and Se tions 15
and 16).
von der Linden and Hors h. von der Linden and Hors h [122 onsider a N -parameter
plasmon-pole model derived from the eigenvalue de omposition of the symmetrized diele tri
0

21

For a known diele tri onstant the above equation at ! =0 de nes !gap .
To in lude lo al- eld e e ts { in parti ular the variation of the s reening hole depth as
a fun tion of the lo ation of an added ele tron { and the orre t symmetry of the s reening
potential under ex hange of r and r0 , Hybertsen and Louie [113 onsider a s reening potential
that is the sum of the lo al Levine-Louie potentials evaluated at r and r0 (see Eq. (56) below).
They evaluate the homogeneous Levine-Louie s reened potential

W LL (r

r0 )

= ["LL 1 (r

r00 ; rs (r00 ))v (r00 ; r0 )dr00

(54)

at the lo al density determined by rs(r0 ) and use the Levine-Louie gap parameter to ensure
orre t long-range s reening
! 2 (rs ) = ! 2 (rs)=("(0) 1):
(55)
gap

pl

Here "(0) is the stati diele tri onstant and an input parameter to the model. Hybertsen
and Louie [113 expli itly symmetrize the s reening potential
1
W HL (r; r0) = [W LL (r r0 ; rs(r0 )) + W LL (r0
2
whi h leads to the following expression in re ipro al spa e

r; rs (r));

(56)

Z
1
1
0

(
q
;
!
=
0)
v
(
q
+
G
)
=
v
(
q
+
G
)
["LL 1 (jq + Gj; rs (r0 ))ei(G G)r dr0
GG
2

Z
+ v (q + G0 ) ["LL 1 (jq + G0 j; rs(r))ei(G G)rdr : (57)

["HL

The diagonal part of the Hybertsen-Louie diele tri matrix is given as the average over the
lo al Levine-Louie s reening response at di erent points in the rystal. The HybertsenLevine-Louie model has been applied to a variety of bulk semi ondu tors and interfa es (see
Se tions 19 to 22). It generally reprodu es results of full RPA al ulations for quasiparti le
energies to within 0.1 to 0.4 eV for states lose to the band gap [113, 114.
b. Plasmon-pole models
The imaginary part of the important matrix elements of the diele tri matrix has a peaked
stru ture as a fun tion of frequen y, whi h plasmon-pole models approximate by a -fun tion
hara terized by two parameters: the e e tive strength and the e e tive frequen y of the
plasmon ex itation. Together with the independent-parti le propagator (Eq. (15)), whose
frequen y dependen e is straightforward, plasmon-pole models allow an analyti evaluation
of the onvolution of G and W in frequen y spa e (Eq. (35)). As a onsequen e, the numeri ally expensive integration in Eq. (35) is avoided.
Plasmon-pole models give a good des ription of both the low-energy behavior of the
diele tri matrix { via reprodu tion of the stati limit { and the high-energy behavior of
20

onstant for small- and medium-gap semi ondu tors [104. As is shown in Fig. 7 for Si and
GaAs, the model by Cappellini et al. gives a better des ription of the full RPA diele tri
fun tion than the Levine-Louie model whi h is introdu ed below. However, in ontrast to
the Levine-Louie model, the model of Cappellini et al. does not redu e to the RPA diele tri
fun tion in the ase of metalli s reening. For an appli ation of the model in the ontext of
GWA see, for example, Ref. [108.
COHSEX al ulations for insulators in the 1970s and early 1980s (see Se tion 9 a) often
relied on the Penn diele tri fun tion [109 and its variations, whi h des ribe the diele tri
response of an isotropi , three-dimensional, insulating ele tron gas. Penn [109 uses the
Ehrenrei h-Cohen formula [110 for the diele tri response fun tion. With Egap as an average
opti al gap that is adjusted to t "(q = 0) with the experimental diele tri onstant, EF
as the Fermi energy and kF as the Fermi ve tor the numeri al results an be tted with an
interpolation formula [111, 112
!
#
"
!pl 2
EF  q 2 1=2 1=2
(50)
"(q ) = 1 +
F
F 1+
Egap
Egap kF
where the fa tor F is given by

Egap 1  Egap 2
F =1
:
(51)
+
4 E F 3 4 EF
Modi ations of the Penn model based on a more ompli ated band stru ture have been
suggested [111, 112 and applied to stati COHSEX al ulations (see Se tion 9 a).
In the same spirit as the Penn model, the Levine-Louie diele tri fun tion [106 modi es
the RPA diele tri fun tion by an ad ho introdu tion of an energy gap in the spe trum of the
homogeneous ele tron gas. This model diele tri fun tion (i) interpolates smoothly between
the s reening properties of a metal and an insulator, (ii) reprodu es the numeri al results of
Walter and Cohen [105 for the stati diagonal diele tri matrix in Si well as shown in Fig. 7,
(iii) ful lls important sum rules su h as the f-sum rule, (iv ) has the orre t long-wavelength
behavior, and (v ) negle ts lo al- eld e e ts. Sin e semi ondu tors and insulators annot
absorb light with energies below the fundamental band gap, Levine and Louie introdu e the
band gap in an ad ho fashion into the imaginary part of the RPA diele tri fun tion via
(

Im "RP A (q; ! ); j! j  !gap


0; j! j < !gap

!2 = !2

2 ; sgn(! ) = sgn(! ):
!gap
(52)
This approa h results in a diagonal model diele tri fun tion that depends only on two
parameters: the average ele tron density given by the ele tron gas parameter rs, whi h
determines the plasmon frequen y !pl , and the lowest ex itation frequen y !gap . In the
long-wave-length limit (q ! 0) one nds
!2
"(q ! 0; ! ) = 1 + 2 pl 2 :
(53)
!gap !

Im "LL (q ; ! ) =

19

These indu ed dipoles will in turn intera t with and s reen the ele tron. This s reening
me hanism is non-lo al in real spa e [95. Clearly, model diele tri matri es must a ount
for the gap in the ex itation spe trum and the qualitatively di erent s reening of insulators.
In the ontext of COHSEX al ulations (see Se tion 9), stati model diele tri fun tions
are often used. Fair agreement between experimental and al ulated dire t energy gaps is
a hieved due to a signi ant error an ellation between the negle t of lo al- eld e e ts and
the negle t of the energy dependen e of diele tri s reening.
The model diele tri fun tion used by Lundqvist [98 for the determination of self-energy
orre tions of jellium and simple metals (e.g., potassium, see, for instan e, Ref. [99) (i) redu es to a single plasmon in the limit q ! 0, (ii) des ribes independent-parti le ex itations
for large q , (iii) redu es to Thomas-Fermi s reening for intermediate q , and (iv ) ful lls important sum rules like the f-sum rule. Lundqvist's [98 single-plasmon-pole-model diele tri
fun tion is
!pl2
"(q; ! ) = 1
(48)
! 2 + !pl2 ! 2 (q )
where !pl = (4n0 (0))1=2 is the plasmon frequen y of the system and n0 (0) the G = 0
omponent of the unperturbed density. With vF as Fermi velo ity, the plasmon dispersion
is approximated by ! 2 (q ) = !pl2 + vF2 q 2 =3 + (q 2 =2)2 . The ontinuous spe trum of density
u tuations is substituted by a single plasmon pole and in parti ular ele tron-hole ex itations
are negle ted. In the ase of the homogeneous ele tron gas, Lundqvist [98, 100, 101 shows
that ele tron-hole ex itations are of minor importan e for the determination of the self-energy
.
In inhomogeneous semi ondu tors su h as Si quasiparti le energies determined using
plasmon-pole models (e.g., Ref. [42) di er from those determined by taking the full frequen y
dependen e of "GG (q; ! ) into a ount [102, 103 by no more than 50 meV for the dire t gap
at . Table 21 shows that the valen e band width in Si is about 0.3 eV smaller when
the full frequen y dependen e is taken into a ount ( ompare al ulations by Fleszar and
Hanke [102 and Rieger et al. [103 with plasmon-pole model al ulations [42). The e e t
of parti le-hole ex itations on quasiparti le energies is not signi antly larger than typi al
numeri al un ertainties of GWA al ulations (see Se tions 15, 16, and 18).
A modi ation of the Lundqvist model for semi ondu tors [104 (i) redu es to the stati
diele tri onstant for q ! 0, (ii) reprodu es free-ele tron behavior at large q , (iii) des ribes
a modi ed Thomas-Fermi s reening at intermediate q , and (iv ) allows for the analyti evaluation of the stati Coulomb-hole ontribution to the self-energy. Cappellini, Del Sole,
Reining, and Be hstedt [104 suggest the following expression for the diele tri fun tion of a
semi ondu tor
"
#

q 2 q 4 1
1
"(q ) = 1 + ("(0) 1) +
+ 2
;
(49)
kT F
4!pl
0

where the Thomas-Fermi wave ve tor kT F depends on the ele tron density n and "(0) is the
stati RPA diele tri onstant. The parameter is taken as a tting parameter to optimize agreement with rst-prin iples diele tri onstants and turns out to be approximately
18

within a few hundreds of an eV for states lose to the Fermi level and to within a few tens
of an eV for states whose energy is on the order of the plasmon energy of the given material.
This statement is true if the stati diele tri matrix, whi h is an input parameter to all
plasmon-pole models, is determined from rst-prin iples using DFT rather than from model
diele tri matri es.
This review fo uses on the results of a urate rst-prin iples al ulations of the self-energy
 sin e these al ulations form a onsistent framework for the dis ussion of self-energy e e ts.
Results using model diele tri fun tions will be used as supplementary material or in ases
where no rst-prin iples al ulations exist.
Similar to model diele tri fun tions, models for the self-energy  or the band gap orre tion  are based on well-founded physi al insights into the e e ts of orrelation in solids
but their a ura y is often limited leading to semiquantitative results. A review of simpli ed
GWA al ulations based on models for either the diele tri fun tion or the self-energy an
be found in Ref. [14.
a. Model diele tri fun tions
Models for the stati diele tri matrix must des ribe (i) plasmon ex itations whi h dominate
s reening for small re ipro al latti e ve tors, and (ii) ele tron-hole ex itations whi h ful ll
the f-sum rule at large re ipro al latti e ve tors where s reening is less e e tive. Plasmons
are olle tive oherent ex itations of the ele tron gas whi h result from s reening and an
be visualized as ma ros opi density u tuations. In Fig. 6 areas in (q; ! )-spa e in whi h
the imaginary part of the diele tri fun tion of the intera ting homogeneous ele tron gas
is nonzero are shown s hemati ally. Besides the ontinuum of parti le-hole ex itations the
imaginary part is nonzero at the plasmon energy !pl (q ). For small wave ve tors q , 0  q  q ,
where q is a ut-o ve tor, the plasmon is the dominant ex itation and exhausts the f-sum
rule to more than 90% [93. Close to q , the plasmon os illator strength drops rapidly to
zero and parti le-hole ex itations be ome important. For large wave ve tors (q  2kF )
the spe trum onverges towards the independent-parti le spe trum sin e s reening be omes
less and less e e tive. A good model should therefore interpolate between the plasmon
(0  q  q ) and the parti le-hole (q  2kF ) ex itation hannels.
Model diele tri matri es for real rystals must also apture important features that
determine s reening su h as density inhomogeneities and the existen e of an energy gap in
the ex itation spe trum. Non-zero o -diagonal matrix elements are needed to a ount for
lo al- eld e e ts (see Se tions 10 and 31). Also, the dynami al response of an ele tron to
u tuations in the density n(r) from its mean value is qualitatively di erent in a metal and
a semi ondu tor or insulator. In a metal, the Coulomb potential of a parti le is s reened
very e e tively by the ele tron gas, and the long-range Coulomb potential is turned into a
short-range intera tion that depends on the lo al ele tron density. In a semi ondu tor or
insulator the Coulomb potential is not ompletely s reened by the ele tron gas. For example,
onsider the ase of an additional ele tron lo alized in a bond (i.e., an N + 1 rather than
the original N ele tron system). This ele tron will indu e dipoles in neighboring bonds [94.
17

via Eq. (22) without further iteration. The main task is to nd a single-parti le Hamiltonian H^ 0 whose wave fun tions and energies result in a good single-parti le Green fun tion
(Eq. (15)) and a good s reened intera tion (Eqs. (25), (31), and (33)). Common hoi es for
H^ 0 are LDA or Hartree-Fo k. Although this strategy does not orrespond to a onsistent
determination of self-energy orre tions starting from Hartree theory [87, it has been applied with onsiderable su ess for the determination of band stru tures of semi ondu ting
and metalli materials (see Chapters IV and V).
Cal ulated quasiparti le orre tions to an LDA band stru ture agree in general well with
experiment and have the additional advantage that the LDA potential is lo al { allowing
numeri ally inexpensive al ulations { and that the LDA wave fun tions are lose to quasiparti le wave fun tions. Many-body orre tions to the LDA Hamiltonian are determined
by the expe tation value of the operator (r; r0 ; E ) Vx (r) (r r0 ). An overlap lose to
unity between LDA and quasiparti le wave fun tions has, for example, been reported for Si
[44, 90. As a onsequen e, the self-energy operator is for all pra ti al purposes diagonal
in the LDA basis, whi h an be motivated by Eq. (37). Diagonal matrix elements hkjjki
ontain sums over positive de nite matrix elements jhkjVm jkij2, whereas o -diagonal matrix elements hkjjli, k 6= l, ontain sums over terms proportional to hkjVm jiihijVm jli, i.e.,
over terms with varying phases, whi h potentially an el [27. Note, however, that overlaps small ompared to unity have been observed, for instan e, in transition metals [68 and
transition-metal oxides [50, 54, 55, 91. The disadvantage of using an independent-parti le
Hamiltonian in the LDA is that density fun tional theory is non-perturbative in nature. Systemati improvements of GWA al ulations based on LDA Hamiltonians are only feasible
on e self- onsisten y is a hieved.
In ontrast to LDA, Hartree-Fo k al ulations provide a good single-parti le basis only
for weakly-polarizable materials and are numeri ally expensive due to the non-lo ality of the
ex hange kernel. Hartree-Fo k Hamiltonians were used as independent-parti le Hamiltonians in the 70's and 80's to study self-energy orre tions in rare earth and ioni solids (see
Se tion 9 a). Current uses of Hartree-Fo k wave fun tions and energies as input for GWA
al ulations are limited to the study of trans-polya etylene (see Se tion 25 b).
8. DETERMINATION OF THE DYNAMICALLY SCREENED INTERACTION
The determination of the dynami ally s reened intera tion and the diele tri matrix in re ipro al spa e as a fun tion of frequen y is numeri ally expensive and an be drasti ally
simpli ed by (i) modeling "GG (q; ! = 0) via model diele tri matri es, and by (ii) modeling the frequen y dependen e of "GG (q; ! ) via plasmon-pole models. The omputational
e ien y of model diele tri fun tions and matri es is o set by a loss in a ura y whi h
limits the use of model diele tri fun tions to systems whose quasiparti le energy shifts are
larger than the a ura y of the model. The approximation of the imaginary part of the
inverse diele tri matrix as a fun tion of frequen y by a simple pole, whi h is the ommon
approximation made in plasmon-pole models (see Fig. 5), is less severe. As is dis ussed
below and in onne tion with Table 21, Se tion 18, plasmon-pole models are a urate to
0

16

With these equations, the interpretation of COH and SEX is lear. The fa tor 1/2 in COH
results from the adiabati turn-on of the intera tion.
Core + valen e. Under the assumption that one an energeti ally and spatially separate
ore ele trons from valen e ele trons in a material, the self-energy equals the sum of the bare
ore-ex hange potential, the s reened ore-polarization potential, and the valen e ele tron
self-energy, all of whi h will be de ned below. Separating the Green fun tion, the s reened
intera tion, and the irredu ible polarizability into a ore and a valen e ontribution

G = G + Gv ;

W = W + Wv ;

P = P + Pv ;

(45)

the self-energy  in the GWA an be expressed as


 = GW = G W + Gv W + Gv Wv  G W + Gv Wv P Wv + Gv Wv :

(46)

Here, we assume that the ore polarizability is negligible in omparison to the valen e polarizability and expand W in terms of the ore polarizability

W = Wv + Wv P Wv + Wv P Wv P Wv + :::  Wv + Wv P Wv :

(47)

The three terms in Eq. (46) an be identi ed as the ex hange potential from the ore (G W 
G v due to the large energy denominators involved, ompare Refs. [83, 84, 85), as the
s reened polarization potential from the ore (Gv Wv P Wv ) and as the self-energy of the
valen e ele trons (Gv Wv ).
A lo al density approximation of the bare ore-ex hange and the s reened ore-polarization
potential leads in general to small errors ex ept for deviations on the order of 0.3 to 0.4 eV in
the band gap of materials with large, soft ores whose lowest ondu tion band state is lo alized on the ioni ores. The non-lo al bare ore-ex hange and the s reened, energy-dependent
ore-polarization potential are generally small as dis ussed, for example, by Hybertsen and
Louie [44. Estimates for atomi Na [4 or solid Al [86 indi ate that both terms ontribute
approximately 1 eV relative to the bottom of the valen e band to the quasiparti le energies.
In GWA al ulations based on the LDA the proper ore-valen e terms are repla ed by an
LDA ex hange- orrelation potential, whi h leads to a mu h smaller error. For states that are
lo alized on large, soft ores su h as the 02 ondu tion band state in Ge, the lo al, energyindependent approximation to the ore-valen e ex hange and orrelation breaks down and
leads to states that are systemati ally too low in energy. Better treatments of ore-valen e
ex hange and orrelation via (i) use of ore-polarization potentials, and (ii) expli it in lusion
of ore states into the valen e band, are des ribed in Se tion 12.
7. DETERMINATION OF THE SINGLE-PARTICLE GREEN FUNCTION
Most urrent GWA al ulations do not attempt a numeri ally expensive, self- onsistent al ulation of G and W but determine good approximations for the single-parti le propagator
and the s reened intera tion separately, i.e., these al ulations adopt a \best G, best W "
philosophy. On e the \best" G and the \best" W are hosen the self-energy is determined
15

Coulomb hole + s reened ex hange (COHSEX). The COHSEX approximation is a physi ally motivated separation of the self-energy into a Coulomb-hole (COH) and a s reenedex hange (SEX) part whose stati limit (i) has been used extensively to orre t Hartree-Fo k
band stru tures, (ii) produ es dire t band gaps to within 20% of experiment but gives a less
reliable a ount of indire t band gaps (see Se tion 9), (iii) allows an examination of lo al eld e e ts on and the energy dependen e of the self-energy. Consider the onvolution in
energy spa e of G and W given by Eq. (35). This onvolution an be determined formally
by introdu ing the spe tral fun tion B (r; r0 ; E ) of the s reened intera tion W in analogy to
the spe tral representation of the Green fun tion in Eq. (13). One an express the s reened
intera tion in terms of B (r; r0 ; E ) { B is an antisymmetri fun tion of energy { as [4

W (r; r0; E ) = v (r; r0) +

1 2E 0 B (r; r0 ; E 0 ) 0
dE
0 E 2 (E 0 i )2

(39)

where = 0+ . The real part of the self-energy  an then be written as the sum of a
Coulomb-hole ontribution COH arising from the poles of the s reened intera tion and a
s reened-ex hange ontribution SEX arising from the poles of the Green fun tion
Re = COH + SEX :

(40)

Using the independent-parti le Green fun tion G0 (Eq. (15)) one an show that
COH (r; r0; E ) =
SEX (r; r0; E ) =

i (r)i (r0 )P

dE 0

B (r; r0 ; E 0 )
E "i E 0

i (r)i (r0 ) Re(W (r; r0; E

"i ))

(41)
(42)

whi h illustrates the interpretation of SEX as a dynami ally s reened ex hange intera tion.
The stati COHSEX approximation assumes in ontrast to the GWA that the s reened
intera tion is instantaneous, i.e., that retardation e e ts an be negle ted. Hen e W is proportional to a -fun tion in time and equal to a onstant in energy spa e. In the stati
COHSEX approximation, the Coulomb hole ontribution to the self-energy equals the intera tion of an ele tron with the indu ed potential due to rearrangement of the other ele trons.
The s reened ex hange ontribution equals the stati ally s reened ex hange energy of the
quasiparti le. To see this, one takes the limit of E "i ! 0. In Eq. (42) this limit implies
the negle t of E "i in omparison to the poles of the s reened intera tion W , whi h are
given by the plasmon energies. This approximation should be reasonable for states lose to
the Fermi energy whi h is veri ed by a tual al ulations (see Se tion 9 a). One nds
COH (r; r0) =
SEX (r; r0) =

1
(r
2

r0 )[W (r; r0 ; E

= 0) v (r; r0);

i (r)i (r0 )W (r; r0; E = 0):


14

(43)
(44)

and using Eq. (30) for the inverseRdiele tri matrix leads to an expression of C (E ) in terms
of u tuation potentials Vm (r) = v (r; r0)nm (r0 )dr0 , ele tron-hole energies "m = EN;m EN;0 ,
and single-parti le energies "i [27:
i Z
C
0
exp(iE 0 )[W (r; r0; E 0 ) v (r r0 )G0 (r; r0; E + E 0 )dE 0
 (r; r ; E ) =
2
o X V (r)V  (r0 ) (r) (r0 ) uno
X
X X V (r)V  (r0 ) (r) (r0 )
m
i
m
i
m
i
m
i
=
+
:
E
+
"
"
i
E
"
"
+
i
m
i
m
i
i m6=0
i m6=0
(36)
The expe tation value of C with respe t to single-parti le orbitals k  jki and l  jli
equals
o X hk jV jiihijV  jli
uno
X
X X hk jV jiihijV  jl i
m
m
m
m :
hkjC (E )jli =
+
(37)
E
+
"
"
i
E
"
"
+ i
m
i
m
i
i m6=0
i m6=0
Energy-dependent orrelations de rease the Hartree-Fo k band gap by raising the valen eband energy and lowering the ondu tion-band energy as an be seen by onsidering the
above equations. For a valen e ele tron in the highest o upied state, jvbi, the largest
ontribution to hvbjC (E = Evb )jvbi omes from the sum over o upied states. For these
states jEvb "i j is small ompared to the ele tron-hole energy "m , whi h is on the s ale of
the Hartree-Fo k energy gap. Hen e the polarization ontribution to the self-energy shifts
the valen e-band maximum upwards in energy. For the ondu tion-band minimum, j bi,
the largest ontribution to h bjC (E = E b )j bi omes from the uno upied states, i.e., the
se ond term in Eq. (37), and hen e leads to a redu tion in the ondu tion-band energy.
The orrelation ontribution to the self-energy of an ele tron in a highly ex ited Rydberg
state redu es via Eq. (37) to the lassi al Coulomb energy of the Rydberg ele tron in the
eld of the indu ed ore dipole [4, 26, 27. Assume that the density u tuations rea t
instantaneously to the presen e of the highly ex ited ele tron. The Fourier transform of the
density u tuations is therefore independent of frequen y whi h translates to E "i = 0
in Eq. (36). Summing over i and using ompleteness gives the following expression for the
self-energy
X V (r)V  (r)
m
m
C (r; r0; E = 0)  (r r0 )
 2 r4 (r r0)
(38)
"
m
m6=0
where is the dipole polarizability of the ion ore around whi h the Rydberg ele tron y les.
The last approximate equality follows from a dipole expansion of the Coulomb potential
inside the expression of the u tuation potential in whi h one keeps only the lowest order,
i.e., dipole terms. The above expression equals the lassi al Coulomb energy of the Rydberg
ele tron due to the eld of the indu ed dipole, whi h is adiabati ally swit hed on in the ion
ore. The GWA re overs the relevant lassi al limit for this spe ial ase. Further examples
whose essential physi s is ontained in the GWA are (i) the energy loss per unit time of a
fast ele tron in an ele tron gas, and (ii) the self-energy shift of a ore ele tron in a solid.
These limiting ases are detailed in Refs. [4, 26, 27 and are not dis ussed here.
13

In a tual al ulations the time-ordered diele tri matrix rather than its inverse is determined from the irredu ible polarizability P . The irredu ible polarizability is onne ted to
the diele tri matrix via

"(r; r0; ! ) = (r

r0 )

v (r; r00 )P (r00; r0 ; ! )dr00:

(31)

To des ribe s reening in solids in the time-dependent Hartree or random phase approximation
(RPA), P is repla ed by the independent-parti le polarizability P 0 whi h an be obtained
via the Adler-Wiser formalism [80, 81, 82. If i (r) and "i are as in Eq. (15) and fi are the
orresponding Fermi fa tors, the independent-parti le polarizability is given by
!

fi (1 fi )
fi (1 fi )
:
+
"i "i + ! + i "i "i ! + i

X
P 0 (r; r0 ; ! ) =  (r)i (r) (r0 )i (r0 )

i;i

(32)

In re ipro al spa e one nds for the independent-parti le polarizability with the fa tor two
a ounting for spin
0 (q; ! ) = 2 Xhij exp(i(q + G)  r)ji0 ihi0 j exp( i(q + G0 )  r0 )jii
PGG
V ii
!
fi (1 fi )
fi (1 fi )
(33)
+
"i "i + ! + i "i "i ! + i
0

and for the RPA diele tri matrix

4
0
(34)
jq + Gj2 PGG (q; !):
To be onsistent with the RPA-based GWA, the energies "i should in prin iple be al ulated
from a Hartree Hamiltonian. However, an LDA spe trum is generally used instead for onvenien e, as des ribed further in Se tion 7.
A
"RP
GG (q; ! ) = GG
0

6. SEPARATION OF THE SELF-ENERGY


The energy-dependent GWA self-energy is a produ t of the propagator G and s reened
intera tion W in real spa e as a fun tion of time (see Eq. (22)) whi h turns into a onvolution
in frequen y spa e:
i Z iE
e G(r; r0 ; E + E 0 )W (r; r0; E 0 )dE 0 :
(35)
(r; r0 ; E ) =
2
Below, this equation is used in onjun tion with Eq. (15) for the independent-parti le propagator to derive three possible, approximate (G0 is used instead of G) ways of separating
the full self-energy  into physi ally meaningful pie es.
Energy-dependent orrelation + bare ex hange. The energy-dependent orrelation ontribution C (E ) des ribes self-energy e e ts beyond the bare ex hange or Hartree-Fo k ontribution X . Subtra ting the Hartree-Fo k ex hange potential from the self-energy operator
0

12

intera tions, i.e., ladder diagrams, auses the failures of RPA-based GWA al ulations. Improvements for absorption spe tra an be obtained by going beyond RPA-based GWA al ulations and in luding vertex orre tions in the diele tri matrix and the self-energy as is
detailed in Se tions 9b, 14, and 24. Improvement of satellite spe tra and ex hange splittings has re ently been obtained by ab initio umulant expansions [77 and by an ab initio
T -matrix approa h [71. For a review of these approa hes, see, for instan e, Ref. [14.
The diele tri matrix. The s reened intera tion W an also be expressed in terms of the
inverse diele tri matrix " 1 , whi h des ribes s reening in a solid when lo al elds due to
density inhomogeneities and many-body e e ts are taken into a ount. Rather than using
the integral equation Eq. (23), W an be determined as a onvolution of the inverse diele tri
matrix with the bare Coulomb intera tion in real spa e

W (r; r0; ! ) =

" 1 (r; r00 ; ! )v (r00; r0)dr00 :

(25)

The de nition of the spatial Fourier transform as

"(r; r0 ; ! ) =

1
V

ei(q+G)r "GG (q; ! )e i(q+G )r ;


0

q;G;G0

(26)

with q a ve tor in the re ipro al spa e Brillouin zone and G, G0 as re ipro al latti e ve tors
allows the transformation of the above onvolution in real spa e into a simple multipli ation
in re ipro al spa e
4
1
WGG (q; ! ) =
(27)
jq + Gj2 "GG (q; !):
The o -diagonal elements "GG (q; ! ), G 6= G0 , des ribe s reening due to an inhomogeneous
density distribution, i.e., the lo al- eld e e ts [78 (see Se tions 10 and 31).
Expressing the inverse diele tri matrix in terms of density u tuations [27, 79 allows
a simple interpretation of orre tions to Hartree-Fo k theory by the energy-dependent orrelation ontribution to the self-energy (see also next se tion). Let jN; 0i (jN; mi) be the
ground (ex ited) state of an N -ele tron system, n^ 0 the density u tuation operator
0

^ y(rt) (
^ rt)
n^ 0 (rt) =

^ rt)jN; 0i;
hN; 0j ^ y(rt) (

nm (r) = hN; mjn^ 0 (r)jN; 0i a density u tuation, and "m = EN;m


energy. The inverse diele tri matrix is given as [27, 79
" 1 (r; r0 ; t) = (r

r0 ) (t)

i v (r

r00 )

(28)

EN;0 an ele tron-hole

hN; 0jT [^n0(r00 t)^n0(r00)jN; 0idr00

(29)

2"m nm (r00 )nm (r0 ) 00


2 ("m i )2 dr :
m6=0 !

(30)

or after Fourier transform as [27

" 1 (r; r0; ! ) = (r

r0 ) +

v (r
11

r00 )

equations governing the GWA are


(1; 2) = iG(1; 2)WZ(1+; 2);
W (1; 2) = v (1; 2) + W (1; 3)P (3; 4)v (4; 2)d(3; 4);
P (1; 2) = iG(1; 2)G(2; 1):

(22)
(23)
(24)

The dynami ally s reened intera tion approximation or GWA in prin iple requires a self onsistent determination of the single-parti le propagator G and the s reened intera tion
W as shown s hemati ally in Fig. 4, panel b). In pra ti e, su h a determination is omputationally expensive and has only rarely been done as dis ussed in Se tion 13. Further
approximations for the determination of G and W are des ribed in Se tions 7 and 8.
The dynami ally s reened intera tion W introdu es energy-dependent orrelation e e ts.
In parti ular, we analyze in Se tion 6 the self-energy in terms of its bare-ex hange and energydependent orrelation or polarization [64 ontribution. The bare ex hange ontribution to 
results from the bare Coulomb intera tion v (r; r0) = 1=jr r0j, whereas the energy-dependent
orrelation ontribution results from W v . Dynami e e ts in the s reening pro ess are
important sin e moving quasiparti les drag their polarization loud behind them. As a
onsequen e, dynami s reening is less e ient than stati s reening and dire tly a e ts
quasiparti le energies (about a 20% e e t, as noted, e.g., in Ref. [44, see Se tion 11).
The dynami ally s reened intera tion approximation an be applied to weakly polarizable
materials with a diele tri onstant lose to unity and to strongly polarizable solids su h as
the semi ondu tors Si and GaAs with diele tri onstants of order ten. In the former ase,
the GWA redu es to Hartree-Fo k theory, whi h is known to work well for systems su h as
atoms or large-band-gap, low-polarizability solids like rare-gas solids and ioni rystals [65.
In the latter ase, the GWA roughly halves the Hartree-Fo k gap and is lose to experiment.
The energy-dependent orrelation orre tion to Hartree-Fo k theory systemati ally lowers
ondu tion band energies and raises valen e band energies as will be shown in detail in
Se tion 6.
Limitations of the GWA. Several important failures of the GWA have been pointed
out: (i) For ore-level spe tra in atoms, strong ele tron-ele tron intera tion breaks down
the quasiparti le pi ture when single and double ore holes are nearly degenerate [66. (ii)
s ! d promotion energies for the se ond half of the iron series show large dis repan ies with
experiment due to the onset of strong 3d ele tron pairs (see Ref. [67 and Se tion 25 a). (iii)
Ex hange splittings in Ni are about a fa tor two larger than experiment due to the existen e
of strong 3d hole pairs (see Refs. [68, 69 and Se tion 26 ). (iv ) The GWA satellite spe trum
is poor. In the ase of Ni, the 6 eV satellite is missing [68, 69, 70, 71 sin e the GWA does
not apture strong orrelations between 3d holes. The GWA plasmon satellite of a ore
ele tron is 50% too low at 1.5 !pl , where !pl is the plasmon frequen y, rather than at !pl
[72. Even for the homogeneous ele tron gas, the GWA yields a single plasmon satellite
[27, 73, 74, 75 rather than a series of shake-up peaks [76. The same observation holds for
nearly-free-ele tron metals su h as Na and Al [77.
The negle t of vertex orre tions (see Se tion 14) su h as short-ranged parti le-parti le
10

quasiparti le al ulations determine quasiparti le energies via Eq. (17) on e a suitable approximation for the self-energy has been found.
5. THE HEDIN EQUATIONS AND THE GWA
In prin iple, the exa t self-energy an be obtained from a losed set of integro-di erential
equations { the Hedin equations [3, 4 { that in onjun tion with the Dyson equation link
the single-parti le propagator G, the self-energy , and the s reened intera tion W , to the
irredu ible polarizability P and the vertex fun tion whi h will be de ned now. Consider
the appli ation of a small perturbation Vext to the many-body system. The irredu ible
polarizability P is de ned as the hange in the density n upon a hange in the total (external
+ Hartree) eld V = Vext + VH :

P (1; 2) =

n(1)
:
V (2)

(19)

Here 1 is a short notation for a ombined spa e and time oordinate. Similarly, the vertex
fun tion is given by the variation of the inverse Green fun tion with respe t to a hange
in the total potential or, alternatively, by the variation of the self-energy with respe t to V
G 1 (1; 2)
(1; 2)
(1; 2; 3) =
= (1; 2) (1; 3) +
:
(20)
V (3)
V (3)
With the above de nitions, 1+ = (r1 t1 + ), > 0 in nitesimal, and v (1; 2) as bare Coulomb
intera tion, Hedin's equations are
Z

(1; 2) = i G(1; 4)W (1+; 3) (4; 2; 3)d(3; 4);


Z

W (1; 2) = v (1; 2) + W (1; 3)P (3; 4)v (4; 2)d(3; 4);


Z

P (1; 2) = i G(2; 3)G(4; 2) (3; 4; 1)d(3; 4);


Z
(1; 2)
G(4; 6)G(7; 5) (6; 7; 3)d(4; 5; 6; 7):
(1; 2; 3) = (1; 2) (1; 3) +
G(4; 5)

(21)

From these equations, the quasiparti le self-energy an be determined iteratively as is shown


s hemati ally in Fig. 4, panel a).
The simplest, onsistent version of the Hedin equations sets the vertex fun tion to unity
and expresses the self-energy as the produ t of the self- onsistent single-parti le propagator
G and the self- onsistent dynami ally s reened intera tion W . The GWA is onsistent in
the sense that it is a parti le- and energy- onserving approximation or, in other words, a
onserving approximation in the Baym-Kadano sense [62, 63. The GWA orresponds to
the rst iteration of the Hedin equations, i.e., higher-order vertex orre tions are not in luded
(for a dis ussion of vertex orre tions see Se tion 14), and an be interpreted as the rstorder term of an expansion of the self-energy  in terms of the s reened intera tion. The
9

Negle t of ex hange and orrelation e e ts beyond the Hartree approximation leads


to the non-intera ting single-parti le Hamiltonian H^ 0 whose orresponding Green fun tion
G0 (r; r0; E ) des ribes the propagation of a parti le in a system of N +1 non-intera ting parti les. With the omplete set of orthonormalized single-parti le wave fun tions i (r) and
real, independent-parti le energies "i , we write the spe tral representation of G0 as follows
Z
X  (r) (r0 )
A0 (r; r0 ; E 0 ) 0
i
i

dE :
(15)
G0 (r; r0 ; E ) =
E "i
C E E0
i
The independent-parti le spe tral fun tion an either be expressed as in Eq. (14) with i
being repla ed by i or in the basis of the orthonormalized i . In the latter ase, A0 redu es
to a -fun tion, A0i = (E "i ).
The time development of the intera ting Green fun tion is determined by the quasiparti le
self-energy via Dyson's equation [19. With G and G0 as in Eqs. (13) and (15) we have [19

G(r; r0 ; E ) = G0 (r; r0 ; E ) +

ZZ

G0 (r; r1; E )(r1; r2 ; E )G(r2; r0 ; E )dr1dr2;

(16)

where (r; r0 ; E ) is the non-lo al, energy-dependent, non-Hermitian self-energy introdu ed


in the previous hapter. As mentioned earlier,  a ounts for all ex hange and orrelation e e ts beyond the Hartree approximation. The above equation an also be written
symboli ally as G 1 = (G0 ) 1 .
Instead of determining the quasiparti le energies indire tly as poles of the Green fun tion,
it is more onvenient to obtain these energies as solutions of the quasiparti le equation.
The quasiparti le equation an be derived by inserting the spe tral representation of the
intera ting Green fun tion into Dyson's equation and is given in Eq. (3). It is formally
similar to the single-parti le equation of Kohn-Sham theory (Eq. (9)) but the solutions
of the quasiparti le equation, i.e., the quasiparti le energy Ei and wave fun tion i , are
physi ally meaningful rather than mere mathemati al tools as is the ase in DFT.
Whenever possible one hooses as a starting point a suitable independent-parti le Hamiltonian whose wave fun tions i (r) are nearly identi al with the quasiparti le wave fun tions
i (r), whi h hoi e allows the determination of quasiparti le energies via rst-order perturbation theory. Assume H^ 0 = r2 =2 + VH + Vext + Vx as in Eq. (9) with hi j i i  1. Then
the quasiparti le energy must be determined self- onsistently from

Ei = "i + hi j(Ei ) Vx ji i  "i + Zi hi j("i ) Vx ji i;


where the quasiparti le weight Zi is de ned as
2
3 1




(
E
)
i

5
Z i = 41

; i (E )  hi j(E )ji i:
E E ="

(17)

(18)

The linear expansion of the self-energy with respe t to energy needed to derive the approximate relationship in Eq. (17) is well justi ed as will be detailed in Se tion 11. Most urrent
8

II. Quasiparti le al ulations in the GW approximation


This hapter has four purposes: (i) The basi equations that govern the dynami ally s reened
intera tion approximation are introdu ed (Se tions 4 and 5) but not derived. We refer the
reader to standard text books, for example, Ref. [20, and the review arti les by Hedin
and Lundqvist [4 and Aryasetiawan and Gunnarsson [14, in parti ular, for a derivation
of the Hedin equations (Se tion 5). (ii) Useful separations of the self-energy as well as
basis-set-independent details about the evaluation of the single-parti le propagator G and
the s reened intera tion W are des ribed in Se tions 6 to 8. (iii) Se tion 9 gives a histori al
overview of early GWA al ulations and related approa hes. (iv ) The physi s of the selfenergy operator is analyzed in Se tions 10 to 14 with Se tions 13 and 14 fo using on the
onsisten y of GWA al ulations and on extensions to the GWA, respe tively. An overview of
important equations for the GWA and symbols used in this arti le is given in Tables 1 and 2.
4. THE QUASIPARTICLE EQUATION
The physi al relevan e of the Green fun tion [60 (Eq. (5)) an be made lear by expressing
G in terms of quasiparti le wave fun tions and energies via its spe tral fun tion A. Consider
a omplete set of eigenstates of the many-body Hamiltonian for a system with N +1 or N 1
parti les. Let  be the hemi al potential and denote the quantum number of the (N +1)parti le or (N 1)-parti le states with i. With EN;i as the energy of the N -ele tron system
in state i (i=0 for the ground state), one de nes the quasiparti le amplitude i (r) and the
quasiparti le energy Ei as [4
^ r)jN + 1; ii; Ei = EN +1;i EN;0 for Ei  ;
i (r) = hN; 0j (
^ r)jN; 0i; Ei = EN;0 EN 1;i for Ei < :
i (r) = hN 1; ij (

(12)

As mentioned above, the quasiparti le amplitudes orrespond to a non-lo al, energy-dependent,


and non-Hermitian Hamiltonian. They ful ll the ompleteness relation but are unnormalized
and linearly dependent [4. Introdu tion of the omplete set of eigenstates in the de nition of
G given in Eq. (5) and Fourier transformation to energy spa e [61 identi es the quasiparti le
energies as the poles of the Green fun tion
X (r)  (r0 )
i
i
G(r; r0; E ) =

Ei

A(r; r0 ; E 0 ) 0
dE :
C E E0

(13)

The integral de nes the intera ting spe tral weight fun tion

A(r; r0 ; E ) 

i (r) i (r0 ) (E

Ei )

(14)

and the integration ontour C runs in nitesimally above the real E 0 -axis for E 0 <  and
in nitesimally below for E 0 > .
7

hom (r), evaluated at the lo al density. The total ex hangea homogeneous ele tron gas, Ux
orrelation energy is then obtained as the integral over all lo al ontributions:
LDA =
Ex

n(r)Ux hom (r)dr:

(11)

The resulting ex hange- orrelation potential is lo al and energy-independent. Despite its


simpli ity, the lo al density approximation and extensions that use gradient orre tions to
the lo al density { the generalized gradient approximations { su essfully des ribe groundstate properties of atoms, mole ules, and solids. This su ess and also several failures of
LDA are reviewed extensively in the literature, see, for instan e, Refs. [37, 38. Stru tural
properties of solids su h as the latti e onstant, the bulk modulus, and the ohesive energy
are generally determined to within a few per ent of the experimental value.
The band-gap problem. In the derivation of Kohn-Sham theory [33, the eigenvalues "i in
Eq. (9) enter as Lagrange parameters that ensure the orthogonality of the orbitals i of the
titious parti les. As a onsequen e, the "i 's and i 's must be onsidered as mathemati al
tools that ontain no relevant physi al information besides the fa t that the square of the
eigenfun tions sums up to the exa t lo al ground-state density. In parti ular, there is no
formal justi ation that links the eigenvalues "i to the energy dispersion of quasiparti les in
a solid. A notable ex eption is the highest o upied eigenvalue "N . Sham and Kohn [39
identify "N with the hemi al potential  of a metal. For semi ondu tors and insulators,
Perdew, Parr, Levy, and Balduz [40 prove that "N equals the negative of the ionization
energy [41.
Perhaps the most prominent dis repan y between LDA band stru tures and experiment
is the fa t that LDA underestimates the band gap of semi ondu tors and insulators by about
0.5 to 2.0 eV. In the ase of Ge, LDA leads to a semimetal rather than to an indire t gap
semi ondu tor. Figure 3 demonstrates the underestimation of experimental band gaps in
LDA for all semi ondu tors and insulators for whi h ab-initio GWA al ulations have been
reported. Figure 3 also shows that GWA al ulations largely orre t the LDA band-gap
underestimation and are in good agreement with experiment. In spite of the band-gap
underestimation, LDA wave fun tions are often good approximations to quasiparti le wave
fun tions [59.
In absen e of quasiparti le al ulations, LDA energies are routinely used to interpret
experimental spe tra. LDA energy dispersions are often in fair agreement with experiment
and in some ases the LDA band gap an be empiri ally adjusted to t the experimental
gap. This approa h implies an interpretation of the LDA ex hange- orrelation potential as
an approximate self-energy whi h negle ts non-lo al, energy-dependent, and life-time e e ts.
Although the LDA band stru ture annot laim quantitative a ura y for the determination
of the ele troni stru ture of solids, LDA generally provides a qualitative understanding.

the quasiparti le life time, these additional e e ts must be in luded (see Refs. [26, 29, 30
and referen es therein).
3. KOHN-SHAM PARTICLES
All GWA al ulations start from a suitably hosen one-parti le Hamiltonian whose eigenfun tions and eigenvalues are used to onstru t the single-parti le propagator G, the s reened
intera tion W , and the self-energy  as will be detailed in Chapter II. The independentparti le Hamiltonian of hoi e [31 is a density fun tional (DFT) Hamiltonian in the lo al
density approximation (LDA) [32, 33. Density fun tional theory des ribes ground-state
properties and, in parti ular, the ground-state density in prin iple exa tly, but does not
des ribe ex ited states a urately. The lo al density approximation to DFT is a pra ti al
starting point for quasiparti le al ulations sin e (i) it des ribes the density of metals, semi ondu tors, and insulators a urately, and (ii) ex hange and orrelation are des ribed by a
lo al potential. Point (i) suggests that LDA ground-state wave fun tions are good approximations for quasiparti le wave fun tions. This is often the ase not only for ground states
but also for ex ited states as is further dis ussed in Se tion 7. Point (ii) leads to omputationally e ient quasiparti le al ulations ompared to quasiparti le al ulations based on
a non-lo al independent-parti le Hamiltonian su h as Hartree-Fo k (see Se tion 7).
The Kohn-Sham formulation of density fun tional theory [34 maps the problem of N
intera ting ele trons onto a system of N non-intera ting, titious parti les { the KohnSham parti les { whi h move in an e e tive potential VKS . The Kohn-Sham potential VKS
is onstru ted to ensure that the ground-state density of the non-intera ting, titious system
equals the ground-state density n0 (r) of the intera ting system. Let i (r) denote an orbital
of the titious parti les and "i the orresponding eigenvalue of the Kohn-Sham Hamiltonian.
With Vext and VH as de ned earlier, the set of single-parti le equations is [36



1 2
r
+ VH + Vext + Vx i = "i i ;
2

n0 =

i=1

jij2:

(9)

Here Vx is the ex hange- orrelation potential whi h is obtained as a fun tional derivative of
the ex hange- orrelation energy Ex

E [n
;
Vx (r) = x
n(r) n(r)=n0 (r)

(10)

and all potentials are evaluated at the ground-state density n0 (r). The ex hange- orrelation
energy, whi h ontains all Coulomb orrelation e e ts beyond the Hartree approximation
and a part of the kineti energy of the intera ting ele trons, is not known expli itly for real
systems [35. Pra ti al use of the Kohn-Sham equations requires good approximations to
the ex hange- orrelation energy and via Eq. (10) of the ex hange- orrelation potential.
The lo al density approximation repla es the inhomogeneous ex hange- orrelation energy
density per parti le at a point r by the ex hange- orrelation energy density per parti le of
5

whi h is losely onne ted to photoemission spe tra. Quasiparti les are identi ed with narrow peaks in the intera ting spe tral fun tion that ontain a signi ant amount of spe tral
strength. The peak position and width determine the quasiparti le energy and inverse life
time; the area under the peak equals the quasiparti le weight. Figure 1 shows a s hemati
pi ture of an intera ting and a non-intera ting spe tral fun tion. The intera ting spe tral
fun tion has an approximate pole at E = E~ + i . If Z is the quasiparti le weight and (E )
a smooth fun tion at E then the Green fun tion an be expressed as
Z
+ (E ):
(7)
G(E ) =
E E
Assuming Z to be real and negle ting the smooth ba kground Im(E ), one obtains the
orresponding spe tral fun tion as

A( E )   1 Z

(E

:
E~ )2 + 2

(8)

Fourier transformation of Eq. (7) into the time domain leads to an exponential de ay of
G / exp( t) whi h identi es as the inverse quasiparti le life time [24. The smaller
is, the longer the quasiparti le lives, and the sharper the orresponding peak in A(E ). The
quasiparti le weight Z equals the area under the Lorentzian [25 and (i) must be on the
order of unity for the quasiparti le to be learly identi able in the spe trum, and (ii) is less
than unity sin e A(E ) is positive de nite and normalized to unity.
Conne tion to experiment. Quasiparti le energies and life times are measured experimentally by dire t or inverse photoemission, whi h removes or adds one ele tron to the system
and orresponds dire tly to the de nition of the Green fun tion in Eq. (5). In dire t photoemission, a photon with energy h impinges on a sample. An ele tron from an o upied
band with energy EV B absorbs the photon energy and be omes a photoele tron whose kineti energy Ekin allows the determination of the initial-state (valen e) energy. From the
s hemati pi ture of the dire t photoemission pro ess in Fig. 2 and measuring the valen e
and ondu tion band energies with respe t to the va uum level we obtain the following energy balan e Ekin = EV B + h whi h gives EV B . Inverse photoemission, the omplimentary
pro ess to dire t photoemission, probes the energy of uno upied states ECB by inje ting an
ele tron into a solid. The ele tron loses its kineti energy Ekin via photon emission before
it omes to rest at a point of lower energy in the ondu tion band. With h as the energy
of the emitted photon, a simpli ed energy balan e of the pro ess reads Ekin = ECB + h .
This relation gives ECB sin e Ekin and h are measured. A s hemati des ription of inverse
photoemission is given in Fig. 2.
The photo urrent in photoemission experiments is losely related to the single-parti le
spe tral fun tion. The intrinsi photoemission spe trum, i.e., the photoemission spe trum
that takes only many-ele tron s attering into a ount, is expe ted to be reliable for the determination of the quasiparti le peak, i.e., the quasiparti le energy [26, 27, 28. However, the
intrinsi spe trum negle ts matrix element e e ts, phonon and defe t s attering, the inhomogeneous surfa e potential, and other ompli ations. For the determination of, for example,
4

The energy di eren e between the quasiparti le and the bare parti le is usually des ribed
by the self-energy  [16, whi h must a ount for all ex hange and orrelation e e ts beyond
the Hartree approximation. The self-energy is a non-lo al, energy-dependent, and in general
non-Hermitian operator, whose properties will be dis ussed in more detail in Se tions 10
and 11. An exa t determination of the self-energy for real systems is not possible, sin e it
ontains all the omplexities of the many-body system. Instead, pra ti al approximations to
the self-energy { su h as the dynami ally s reened intera tion or GWA whi h is the topi of
the present review (see Chapter II) { must be used. The entral equation that governs the
behavior of quasiparti les is the so- alled quasiparti le equation. Negle ting spin degrees of
freedom, this equation an be written as
Z
1 2
[ r + VH + Vext i (r) + (r; r0 ; Ei ) i (r0 )dr0 = Ei i (r):
(3)
2
Here VH is the ele trostati or Hartree potential of the ele trons, i.e., with n as the ele tron
density,
Z
n(r0 ) 0
(4)
VH (r) =
0 dr ;

jr

Vext is the external potential from the ions, and i and Ei are the quasiparti le wave fun tion
and energy, respe tively. We will ome ba k to the quasiparti le equation and de ne i and
Ei in Se tion 4.
The Green fun tion. Quasiparti le properties su h as energies, life times, and expe tation
values of single-parti le operators su h as the density and the total energy of a many-body
system are determined by the single-parti le Green fun tion (see, for instan e, standard
text books su h as Refs. [17, 18, 19, 20, 21, 22). The Green fun tion G is also alled the
single-parti le propagator. With jN; 0i as the ground state of the N -ele tron Hamiltonian
^ rt) = exp(iHt
^ ) (
^ r) exp( iHt
^ ) as the fermion annihilation operator [23 in
in Eq. (1), (
^ y (rt) as the orresponding reation operator, and T as the
the Heisenberg representation,
time-ordering operator, the single-parti le Green fun tion is de ned as
G(rt; r0 t0 ) =

^ rt)
^ y (r0 t0 )jN; 0i
ihN; 0jT [ (
^ rt)
^ y (r0 t0 )jN; 0i; t > t0 :
ihN; 0j (
= :
^ rt)jN; 0i; t0 > t:
ihN; 0j ^ y(r0 t0 ) (
8
<

(5)

For t > t0 (t0 > t) G des ribes the propagation of a parti le (hole) added to the many-body
system des ribed by H^ , i.e., G des ribes the dynami s of the N ! N  1 ex itations in an
N -ele tron system. G is a fun tion of only six spatial degrees of freedom and hen e mu h
more manageable than the N -ele tron wave fun tion whi h depends on 3N spatial degrees
of freedom. Many of the omplexities of the ground-state wave fun tion are eliminated by
taking the expe tation values.
The imaginary part of the Green fun tion determines the spe tral fun tion A
A(r; r0 ; E ) =  1 jImG(r; r0 ; E )j;
(6)
3

GW approximations resulting from the in lusion of self-energy and vertex diagrams beyond
the random phase approximation. Mahan and Plummer [11 dis uss many-body e e ts in
photoemission spe tra of simple sp-bonded metals. Pollmann et al. [12 on entrate on
GWA al ulations for semi ondu tor surfa es. Farid [13 onsiders mathemati al aspe ts of
quasiparti le al ulations. The re ent review of Aryasetiawan and Gunnarsson [14 fo uses
on strongly orrelated d and f ele tron systems and lo al-orbital basis fun tions [15.
The aim of the present review is to dis uss (i) the physi s and extensions of the GWA
(Chapter II), (ii) numeri al aspe ts of GWA al ulations (Chapter III), (iii) appli ations of
the GWA to semi ondu tors and insulators (Chapter IV) and metals (Chapter V), and (iv )
the relevan e of GWA al ulations to opti al response (Chapter VI). Parti ular importan e
is given to semi ondu ting and insulating systems treated in a plane-wave basis. We ompare
all published rst-prin iples GWA al ulations for ve prototypi al semi ondu tors (Si, Ge,
GaAs, SiC, GaN) and show that di eren es between published quasiparti le al ulations
for the lowest ondu tion-band state an be as large as 0.5 to 1.0 eV. We also present for
the rst time parallel algorithms both for re ipro al and real-spa e/imaginary-time GWA
al ulations. In addition, Chapter VII gives a brief overview of alternative methods to
determine ex ited states within density fun tional theory.
The remainder of this hapter introdu es the quasiparti le on ept, de nes the Green
fun tion and the spe tral fun tion (Se tion 2). The latter is important sin e it an be related to photoemission experiments. A short introdu tion to density fun tional theory is
also ne essary, sin e most urrent quasiparti le al ulations start from density fun tional
theory wave fun tions and energies and measure their su ess by the degree of improvement
of ex ited-state properties over the orresponding density fun tional des ription. Se tion 3
provides the basi equations and physi s of density fun tional theory that are relevant for
quasiparti le al ulations. A more detailed overview of the basi on epts of density fun tional theory is given in Appendix A.
2. QUASIPARTICLES
De nition of quasiparti les. The ex itations of a system of strongly intera ting parti les an
often be des ribed in terms of weakly intera ting quasiparti les. In a solid, an ele tron, or
\bare" parti le, repels the other ele trons via the Coulomb potential and, in e e t, surrounds
itself with a positively harged polarization loud. The positive s reening harge and the
bare ele tron form a quasiparti le whi h weakly intera ts with other quasiparti les via a
s reened rather than the bare Coulomb potential. The quasiparti le lifetime is nite sin e
quasiparti les are only approximate eigenstates of the N -ele tron Hamiltonian in Eq. (1).
The residual intera tion between the quasiparti les leads to a omplex energy whose imaginary part is inversely proportional to the quasiparti le life time. That the quasiparti le
on ept works well in solid state systems { in spite of strong intera tions between the bare
parti les { is demonstrated by the su ess of one-parti le theories su h as density fun tional
theory in the lo al density approximation or GWA in the des ription of the stru tural and
ele troni properties of solids.

I. Many-body e e ts in omputational solid state physi s


1. INTRODUCTION AND OVERVIEW
During the last de ade, quasiparti le al ulations have been used su essfully to des ribe
the ele troni ex ited-state properties of solids su h as single-parti le band stru tures and
absorption spe tra. Under the assumption that ele troni and ioni degrees of freedom
an be de oupled, the problem is that of N ele trons in a solid des ribed by the following
Hamiltonian [1
N
N
X
X
1
1
:
(1)
H^ = [ r2i + Vext (ri ) +
i=1 2
i<j jri rj j

Here ri is the oordinate of ele tron i and Vext is an external potential that a ounts for the
intera tion with the nu lei. The last term in the above equation is the Coulomb intera tion
between the ele trons whi h orrelates the motion of the ele trons. As a onsequen e, an
exa t des ription of the many-ele tron problem requires the solution of an equation with 3N
oupled spatial degrees of freedom. For ma ros opi systems, the number of ele trons N is
on the order of Avogadro's number ( 1023 ), so a solution to the N -ele tron problem must
be approximate.
A su essful approximation for the determination of ex ited states is based on the quasiparti le on ept and the Green fun tion method. The Coulomb repulsion between ele trons
leads to a depletion of negative harge around a given ele tron and the ensemble of this
ele tron and its surrounding positive s reening harge forms a quasiparti le. The mathemati al des ription of quasiparti les is based on the single-parti le Green fun tion G, whose
exa t determination requires omplete knowledge of the quasiparti le self-energy  [2. The
self-energy  is a non-Hermitian, energy-dependent, and non-lo al operator that des ribes
ex hange and orrelation e e ts beyond the Hartree approximation.
A determination of the self-energy an only be approximate, and a working s heme for
the quantitative al ulation of ex itation energies in metals, semi ondu tors, and insulators
is the so- alled dynami ally s reened intera tion or the GW approximation (GWA) [3, 4. In
this approximation, the self-energy  is expanded linearly in terms of the s reened intera tion
W
  GW;
(2)
whi h explains the name of the approximation. The GWA for the omputation of quasiparti le energies was proposed by Hedin [3, 4 in 1965. However, not until the mid-eighties was
the approa h applied to large-s ale, numeri al ele troni stru ture al ulations [5, 6. The
resulting ab-initio band stru tures ompare favorably with experiment.
Several reviews of quasiparti le al ulations in the GWA have been published. Ref. [7
is an early review of bulk and surfa e al ulations in the GWA by Hybertsen and Louie.
Be hstedt [8 dis usses the physi s of the GWA in relation to model approa hes for the al ulation of the diele tri response as well as the self-energy. Godby [9 reviews quasiparti le
al ulations for jellium, simple metals, and semi ondu tors. Mahan [10 examines di erent
1

34. FUNCTIONALS BASED ON EXCITED-STATE DENSITIES


35. TIME-DEPENDENT DENSITY FUNCTIONAL THEORY
36. MONTE CARLO CALCULATIONS

Appendix A: Density fun tional theory


a. Universal density fun tionals
b. The Kohn-Sham system
. The band-gap dis ontinuity
d. The ex hange- orrelation hole
e. Coupling- onstant averages
f. Lo al approximations

21. SURFACES
22. DEFECTS
23. PRESSURE
24. EXCITONS
25. ATOMS AND MOLECULES
a. Atoms
b. Mole ules

V. Metals
26. BULK
a. Core-valen e ex hange
b. Alkali metals
. d and f ele tron metals
27. CLUSTERS
28. SURFACES

VI. GWA al ulations and opti al response


29. OVERESTIMATION OF OPTICAL CONSTANTS WITHIN DFT
30. THE \SCISSORS OPERATOR" AND ITS LIMITATIONS
31. LOCAL-FIELD EFFECTS IN OPTICAL RESPONSE
a. De nitions and gauge
b. Numeri al results
32. DENSITY-POLARIZATION FUNCTIONAL THEORY
a. Divergen e of Kx
b. Real materials

VII. Ex ited states within density fun tional theory


33. FUNCTIONALS BASED ON GROUND-STATE DENSITIES

14. VERTEX CORRECTIONS

III. GWA al ulations: Numeri al onsiderations


15. DIFFERENT IMPLEMENTATIONS OF THE GWA
a. Re ipro al-spa e approa h
. Plane waves
. Lo al-orbital basis set
b. Real-spa e/imaginary-time approa h
. The Green fun tion
. The independent-parti le polarizability
16. PLANE WAVES: NUMERICAL DETAILS
a. Use of symmetry
b. Integration of the Coulomb singularity
. Convergen e
d. Choi e of pseudopotentials and plasmon-pole models
e. Obje t orientation
f. E ien y
17. PARALLEL GWA CALCULATIONS
a. Re ipro al-spa e approa h
b. Real-spa e/imaginary-time approa h
18. GWA CALCULATIONS FOR FIVE PROTOTYPICAL SEMICONDUCTORS
a. Sili on
b. Germanium and gallium arsenide
. Sili on arbide and gallium nitride

IV. Semi ondu tors and insulators


19. BULK
a. Band-gap narrowing in Si
b. Transition-metal oxides
. C60 and related systems
20. SUPERLATTICES { INTERFACES { SCHOTTKY BARRIERS
a. Superlatti es
b. Interfa es
. S hottky barriers
3

Quasiparti le al ulations in solids


I. Many-body e e ts in omputational solid state physi s
1. INTRODUCTION AND OVERVIEW

2. QUASIPARTICLES
3. KOHN-SHAM PARTICLES

II. Quasiparti le al ulations in the GW approximation


4. THE QUASIPARTICLE EQUATION
5. THE HEDIN EQUATIONS AND THE GWA
6. SEPARATION OF THE SELF-ENERGY
7. DETERMINATION OF THE SINGLE-PARTICLE GREEN FUNCTION
8. DETERMINATION OF THE DYNAMICALLY SCREENED INTERACTION
a. Model diele tri fun tions
b. Plasmon-pole models
9. EARLY QUASIPARTICLE CALCULATIONS
a. Stati COHSEX al ulations
b. Ex itoni e e ts
. Lo al approa h
d. Quasiparti le lo al density approximation (QPLDA)
10. LOCAL-FIELD EFFECTS AND THE NONLOCALITY OF THE SELF-ENERGY
a. Lo al- elds
b. Nonlo ality of the self-energy
11. ENERGY DEPENDENCE OF THE SELF-ENERGY
12. CORE-POLARIZATION EFFECTS
a. Core-polarization potentials
b. Expli it treatment of ore ele trons
13. SELF-CONSISTENCY
2

Quasiparti le al ulations in solids


Wilfried G. Aulbur, Lars Jonsson, and John W. Wilkins
Department of Physi s
Ohio State University
Columbus, OH 43210-1106