231
[650 G. E. Engel, Y. Kwon, and R. Martin, Phys. Rev. B 51, 13538 (1995).
[651 Density Fun
tional Methods in Physi
s, ed. R. M. Dreizler and J. da Providen
ia,
NATO ASI Series B123 (Plenum Press, New York, 1985).
[652 R. M. Dreizler and E. K. U. Gross, Density Fun
tional Theory, (Springer, New York,
1990).
[653 Density Fun
tional Theory, ed. E. K. U. Gross and R. M. Dreizler, NATO ASI Series
B337 (Plenum Press, New York, 1995).
[654 R. G. Parr and W. Yang, Density Fun
tional Theory of Atoms and Mole
ules (Oxford
Univ. Press, New York, 1989).
[655 Density Fun
tional Theory of ManyFermion Systems, ed. S. B. Tri
key, Adv. Quant.
Chem. 21 (A
ademi
Press, San Diego, 1990).
[656 N. D. Mermin, Phys. Rev. 137, A1441 (1965).
[657 J. F. Janak, Phys. Rev. B 18, 7165 (1978).
[658 J. P. Perdew, in Density Fun
tional Methods in Physi
s, ed. R. M. Dreizler and J. da
Providen
ia, NATO ASI Series B123 (Plenum Press, New York, 1985), p. 265.
[659 J. P. Perdew and M. Levy, Phys. Rev. Lett. 51, 1884 (1983).
[660 L. J. Sham and M. S
hluter, Phys. Rev. Lett. 51, 1888 (1983).
[661 Stri
tly, similarly to the
hemi
al potential, the ex
hange
orrelation potentials at
integer N must also be dened by their limits as the ele
tron number approa
hes N
from below in a system with fra
tional o
upation of the N th KohnSham orbital.
[662 Formally, by applying the theory for fra
tionally o
upied orbitals to the nonintera
ting
KohnSham system one
an prove that the dis
ontinuity in the kineti
energy T0 as
the ele
tron number passes through N is exa
tly equal to the KohnSham band gap.
The intuitive argument in the text relying on the innitesimal dieren
e between the
KohnSham orbitals in the N  and (N + 1)ele
tron systems is not ne
essary.
[663 J. Harris and R. O. Jones, J. Phys. F 4, 1170 (1974).
[664 S. H. Vosko, L. Wilk, and M. Nusair, Can. J. Phys. 58, 1200 (1980).
[665 J. P. Perdew and A. Zunger, Phys. Rev B 23, 5048 (1981).
[666 J. C. Slater, Phys. Rev. 81, 385 (1951); ibid. 82, 538 (1951).
[667 E. Fermi, Z. Phys. 48, 73 (1928).
230
53,
3764
[582 B. F. Levine and C. G. Bethea, Appl. Phys. Lett 20, 272 (1972).
[583 L. Jonsson, Z. H. Levine, and J. W. Wilkins, Phys. Rev. Lett. 76, 1372 (1996).
[584 W. Henrion and F. E
kart, Z. Naturfors
h. 19A, 1024 (1964).
[585 J. E. Adams and W. Haas, in The Physi
s of Selenium and Tellurium, ed. by
W. C. Cooper (Pergamon, New York, 1969), p. 293.
[586 A. Carvallo, C. R. A
ad. S
i. 126, 728 (1898);
ited in D. E. Gray, Ameri
an Institute
of Physi
s Handbook, 2nd ed. (M
GrawHill, New York, 1963).
[587 H. Zhong, Z. H. Levine, D. C. Allan, and J. W. Wilkins, Phys. Rev. Lett.
(1992); 70, 1032(E) (1993).
69,
379
[588 R. Del Sole and E. Fiorino, Sol. St. Comm. 38, 169 (1981).
[589 W, L. Mo
han and R. G. Barrera, Phys. Rev. B 32, 4984 (1985); 4989 (1985).
[590 S. T. Chui, H. Ma, R. V. Kasowski, and W. Y. Hsu, Phys. Rev. B 47, 6293 (1993).
[591 R. Resta, Phys. Rev. Lett. 77, 2265 (1996).
[592 W. G. Aulbur, L. Jonsson, and J. W. Wilkins, Phys. Rev. B 54, 8540 (1996).
[593 X. Gonze, Ph. Ghosez, and R. W. Godby, Phys. Rev. Lett. 78, 294 (1997).
[594 R. M. Martin and G. Ortiz, Phys. Rev. B 56, 1124 (1997).
[595 Ph. Ghosez, X. Gonze, and R. W. Godby, Phys. Rev. B 56, 12811 (1997).
[596 D. Vanderbilt, Phys. Rev. Lett. 79, 3966 (1997).
[597 G. Ortiz, I. Souza, and R. M. Martin, Phys. Rev. Lett. 80, 353 (1998).
[598 R. W. Godby and L. J. Sham, Phys. Rev. B 49, 1849 (1994).
Nagy, Phys. Rep. 298, 1 (1998).
[599 A.
[600 O. Gunnarsson and B. I. Lundqvist, Phys. Rev. B 76, 4274 (1976).
[601 J. B. Krieger, Y. Li, and G. J. Iafrate, Phys.Rev. A 45, 101 (1992); 46, 5453 (1992);
Y. Li, J. B. Krieger, and G. J. Iafrate, ibid. 47, 165 (1993).
[602 R. T. Sharp and G. K. Horton. Phys. Rev. 90, 317 (1953).
[603 J. D. Talman and W. F. Shadwi
k, Phys. Rev. A 14, 36 (1976).
[604 D. M. Bylander and L. Kleinman, Phys. Rev. B 52, 14566 (1995).
227
[561 B. Adolph, V. I. Gavrilenko, K. Tenelsen, F. Be
hstedt, and R. Del Sole, Phys. Rev.
B 53, 9797 (1996).
[562 V. I. Gavrilenko and F. Be
hstedt, Phys. Rev. B 55, 4343 (1997).
[563 R. Del Sole and R. Girlanda, Phys. Rev. B 54, 14376 (1996).
[564 F. Be
hstedt, K. Tenelsen, B. Adolph, and R. Del Sole, Phys. Rev. Lett.
(1997).
78,
1528
[540 J. Chen, Z. H. Levine, and J. W. Wilkins, Phys. Rev. B 50, 11514 (1994).
[541 Z. H. Levine and D. C. Allan, Phys. Rev. B 44, 12781 (1991).
[542 J. Chen, Z. H. Levine, and J. W. Wilkins, Appl. Phys. Lett. 66, 1129 (1995).
[543 H. Zhong, Z. H. Levine, D. C. Allan, and J. W. Wilkins, Phys. Rev. B 48, 1384 (1993).
[544 C. S. Wang and B. M. Klein, Phys. Rev. B 24, 3393 (1981).
[545 M.Z. Huang and W. Y. Ching, Phys. Rev. B. 47, 9449 (1993).
[546 M. Alouani and J. Wills, Phys. Rev. B 1996, 2480 (1996).
[547 S. Bei der Kellen and A. J. Freeman, Phys. Rev. B 54, 11187 (1996).
[548 S.H. Wei and A. Zunger, Phys. Rev. B 39, 3279 (1989).
[549 H. Krakauer, S.H. Wei, B. M. Klein, and C. S. Wang, Bull. Am. Phys. So
. 29, 391
(1984).
[550 B. I. Min, S. Massidda, and A. J. Freeman, Phys. Rev. B 38, 1970 (1980).
[551 Crystal and Solid State Physi
s, Vol. 17A of LandholtBornstein, Numeri
al Data and
Fun
tional Relationships in S
ien
e and Te
hnology, edited by O. Madelung (Springer,
Berlin, 1984).
[552 A. Dal Corso, F. Mauri, and A. Rubio, Phys. Rev. B 53, 15638 (1996).
[553 V. Fiorentini, Phys. Rev. B 46, 2086 (1992).
[554 A. Dal Corso, S. Baroni, R. Resta, Phys. Rev. B 49, 5323 (1994).
[555 A. Dal Corso, A. Pasquarello, A. Balderes
hi, and R. Car, Phys. Rev. B
(1996).
53,
1180
68,
[501 G. Materlik, J. E. Muller, and J. W. Wilkins, Phys. Rev. Lett. 50, 267 (1983).
[502 E. Clementi and C. Roetti, Atomi
Data and Nu
lear Data Tables 14, 177 (1974).
[503 Note that Fig. 42 shows that s
reening of the nonlo
al ex
hange part leads to moderate
quantitative
hanges in the results as does the in
lusion of lifetime ee
ts, i.e., of the
imaginary part of the selfenergy.
[504 N. W. Ash
roft and N. D. Mermin, Solid State Physi
s (Holt, Rinehart, and Winston,
New York, 1976), p. 285 .
[505 E. Jensen and E. W. Plummer, Phys. Rev. Lett. 55, 1912 (1985).
[506 I.W. Lyo and E. W. Plummer, Phys. Rev. Lett. 60, 1558 (1988).
[507 N. D. Lang and W. Kohn, Phys. Rev. B 1, 4555 (1970).
[508 H. J. Levinson, F. Greuter, and E. W. Plummer, Phys. Rev. B 27, 727 (1983).
[509 R. S. Crisp and S. E. Williams, Philos. Mag. 5, 1205 (1960).
[510 E. W. Plummer, Phys. S
r. T 17, 186 (1987).
[511 The results of Refs. [257 and [184 dier by 70 meV leading to 2.52 eV for the quasiparti
le band width as used in Table 32.
[512 The appropriate
hoi
e of vertex
orre
tions is a topi
of
urrent dis
ussions [232, 267.
[513 Note that both Shirley and Northrup et al. use plasmonpole models whi
h may ae
t
the a
ura
y of their
al
ulated valen
e band widths.
[514 See also Ref. [11 for a
riti
al dis
ussion of the theoreti
al determination of the alkali
metal band width.
[515 Further Appli
ations. Re
ently, Kubo reported Compton prole studies of Li and Na
using fullpotential LMTO [287, 288.
[516 F. Aryasetiawan and K. Karlsson, Phys. Rev. B 54, 5353 (1996).
[517 W. A. De Heer, W. D. Knight, M. Y. Chou, and M. L. Cohen, Solid St. Phys. 40, 93
(1987).
[518 P. Fayet, J. P. Wolf, and L. Woste, Phys. Rev. B 33, 6792 (1986).
[519 A. Herrmann, E. S
huma
her, and L. Woste, J. Chem. Phys. 68, 2327 (1978).
[520 M. M. Kappes, M. S
har, P. Radi, and E. S
huma
her, J. Chem. Phys. 84, 1863 (1986).
223
[485 F. R. Vukajlovi
, E. L. Shirley, and R. M. Martin, Phys. Rev. B 43, 3994 (1991).
[486 D. M. Bylander and L. Kleinman, Phys. Rev. B 41, 7868 (1990).
[487 This approa
h modies the LSDA by
onsidering a nonlo
al, s
reened HartreeFo
k
operator as part of the ex
hange
orrelation potential [486. This te
hnique in
ludes
nonlo
ality ee
ts of the quasiparti
le selfenergy but omits its energy dependen
e in
ontrast to GWA.
[488 E. C. Ethridge, J. L. Fry, and M. Zaider, Phys. Rev. B 53, 3662 (1996).
[489 C. G. Van de Walle and J. E. Northrup, Phys. Rev. Lett. 70, 1116 (1993).
[490 M. S. Brandt, H. D. Fu
hs, M. Stutzmann, J. Weber, and M. Cardona, Solid St.
Commun. 81, 307 (1992).
[491 C. R. Fin
her, Jr., M. Ozaki, M. Tanaka, D. Peebles, L. Lau
hlan, A. J. Heeger, and
A. G. Ma
Diarmid, Phys. Rev. B 20, 1589 (1979).
[492 J. Fink and G. Leising, Phys. Rev. B 34, 5320 (1986).
[493 H. Fritzs
he, N. Nu
ker, B. S
heerer, and J. Fink, Synth. Met. 28, D237 (1989).
[494 D. Moses, A. Feldblum, E. Ehrenfreund, A. J. Heeger, T.C. Chung, and A. G. Ma
Diarmid, Phys. Rev. B 26, 3361 (1982).
[495 J. J. Ritsko, E. J. Mele, A. J. Heeger, A. G. Ma
Diarmid, and M. Ozaki, Phys. Rev.
Lett. 44, 1351 (1980).
[496 H. Zs
heile, R. Grundler, U. Dahms, J. Frohner, and G. Lehmann, Phys. Stat. Solidi
B 121, K161 (1984).
[497 The same quasiparti
le
orre
tion is assumed to be valid for the polysilane and the
siloxene
ompound based on the similarity of the highest o
upied and lowest uno
upied state in the two materials. This approximation is
rude, sin
e quasiparti
le shifts
are determined by a sum over a range of o
upied and uno
upied states.
[498 For re
ent reviews on porous sili
on see, for instan
e, P. D. J. Cal
ott, Mat. S
i. Eng. B
51, 132 (1998); A. G. Cullis, J. Appl. Phys. 82, 909 (1997); P. M. Fau
het, J. Lumin.
70, 294 (1996); B. Hamilton, Semi
ond. S
i. Te
hnol. 10, 1187 (1995); G. C. John and
V. A. Singh, Phys. Rep. 263, 93 (1995); and M. H. Ludwig, Crit. Rev. Solid St. Mat.
S
i. 21, 265 (1996).
[499 I. D. White, R. W. Godby, M. M. Rieger, and R. J. Needs, Phys. Rev. Lett. 80, 4265
(1998).
[500 W. Speier, R. Zeller, and J. C. Fuggle, Phys. Rev. B 32, 3597 (1985).
222
[466 K. A. Goettel, J. H. Eggert, I. F. Silvera, and W. C. Moss, Phys. Rev. Lett. 62, 665
(1989).
[467 R. Rei
hlin, K. E. Brister, A. K. M
Mahan, M. Ross, S. Martin, Y. K. Vohra, and
A. L. Ruo, Phys. Rev. Lett. 62, 669 (1989).
[468 A. L. Ruo, H. Luo, and Y. K. Vohra, J. Appl. Phys. 69, 6413 (1991).
[469 The LDA and GWA gaps for h
p H2 with all mole
ules aligned along the
axis are 8.4
and 15.4 eV. When disorder is in
luded via a virtual
rystal approximation the gaps
hange to 8.3 and 15.3 eV
ompared to an experimental value of 14.51 eV [457.
[470 N. H. Chen, E. Sterer, and I. F. Silvera, Phys. Rev. Lett. 76, 1663 (1996).
[471 R. J. Hemley, H.k. Mao, A. F. Gon
harov, M. Han
and, and V. Struzhkin, Phys. Rev.
Lett. 76, 1667 (1996).
[472 R. J. Hemley and N. W. Ash
roft, Physi
s Today 51, 26 (1998).
[473 M. Ross, Phys. Rev. B 54, R9589 (1996).
[474 S. Albre
ht, L. Reining, R. Del Sole, and G. Onida, Phys. Rev. Lett. 80, 4510 (1998).
[475 L. X. Benedi
t, E. L. Shirley, and R. B. Bohn, Phys. Rev. B 57, R9385 (1998).
[476 L. X. Benedi
t, E. L. Shirley, and R. B. Bohn, Phys. Rev. Lett. 80, 4514 (1998).
[477 M. Rohlng and S. G. Louie, Phys. Rev. Lett. 81, 2312 (1998).
[478 Handbook of opti
al
onstants of solids edited by E. D. Palik (A
ademi
Press, Boston,
1991).
[479 E. L. Shirley, Phys. Rev. Lett. 80, 794 (1998).
[480 G. Onida, L. Reining, R. W. Godby, R. Del Sole, and W. Andreoni, Phys. Rev. Lett.
75, 818 (1995).
[481 A. Gorling, private
ommuni
ation.
[482 J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Ja
kson, M. R. Pederson, D. J. Singh,
and C. Fiolhais, Phys. Rev. B 46, 6671 (1992).
[483 W. C. Martin and W. L. Wiese, in Atomi
, Mole
ular, & Opti
al Physi
s Handbook,
ed. by G. W. F. Drake (AIP, Woodbury, NY, 1996), Chapter 10, pp. 135153.
[484 A. A. Radzig and B. M. Smirnov, Referen
e Data on Atoms, Mole
ules, and Ions,
Springer Series in Chemi
al Physi
s 31, (SpringerVerlag, Berlin, 1985).
221
331333,
1152
53,
[455 M. P. Surh, H. Ca
ham, and S. G. Louie, Phys. Rev. B 51, 7464 (1995).
[456 H. Cha
ham, X. Zhu, and S. G. Louie, Europhys. Lett. 14, 65 (1991).
[457 H. Cha
ham, X. Zhu, and S. G. Louie, Phys. Rev. B 46, 6688 (1992).
[458 H. Cha
ham and S. G. Louie, Phys. Rev. Lett. 66, 64 (1991).
[459 M. P. Surh, S. G. Louie, and M. L. Cohen, Phys. Rev. B 45, 8239 (1992).
[460 For a review see F. Siringo, R. Pu
i, and N. H. Mar
h, High Press. Res. 2, 109 (1989).
[461 M. P. Posternak, R. S. Taylor, A. Chen, C. Meade, L. M. Fali
ov, A. Giesekus, R. Jeanloz, and P. Yu, Phys. Rev. Lett. 65, 790 (1990).
[462 X. Zhu, S. Fahy, and S. G. Louie, Phys. Rev. B 39, 7840 (1989).
[463 R. W. Godby and R. J. Needs, Phys. Rev. Lett. 62, 1169 (1989).
[464 B. Welber, C. K. Kim, M. Cardona, and S. Rodriguez, Solid St. Commun.
(1975).
[465 L. Brey and C. Tejedor, Solid St. Commun. 55, 1093 (1985).
220
17,
1021
70,
1685
236,
69,
2947
[413 For a review see for instan
e M. S. Hybertsen, Mat. S
i. Eng. B 14, 254 (1992).
[414 See for instan
e F. Capasso and G. Margaritondo (eds.) Heterojun
tion Band Dis
ontinuities: Physi
s and Appli
ations (North Holland, New York, 1987).
[415 After
performing
an
inplane
R
average of, e.g., the potential V (z ) = 1=S S V (x; y; z )dxdy (S is the inplane area
of the surfa
e unit
ell) an additional \running" average over the extension of a unit
ell in the growth dire
tion (z ) is performed. With a as the latti
e
onstant in the z
R
dire
tion one denes V (z ) = 1=a zz+a=a=22 V (z 0 )dz 0 whi
h redu
es to a
onstant in the
bulk and shows a smooth transition at the interfa
e. For a dis
ussion of these kinds
of averages, see, for instan
e, S. Baroni, R. Resta, A. Balderes
hi, and M. Peressi, in
Spe
tros
opy of Semi
ondu
tor Mi
rostru
tures, edited by G. Fasol, A. Fasolino, and
P. Lugli, NATO ASI Series B Vol. 206 (Plenum Press, New York, 1989), p. 251.
[416 The absolute energy level in GWA
an be shifted by
onvergen
e, the
hoi
e of the
ex
hange
orrelation potential, and the
hoi
e of vertex
orre
tions as detailed in Se
tion 14. The valen
e band oset is determined with the impli
it assumption that the
dieren
e in selfenergy
orre
tions is physi
ally meaningful and independent of te
hni
al details provided that both semi
ondu
tors are treated on the same level of approximation.
[417 S. B. Zhang, D. Tomanek, S. G. Louie, M. L. Cohen, and M. S. Hybertsen, Solid St.
Commun. 66, 585 (1988).
[418 P. Dawson, K. J. Moore, and C. T. Foxon, in Quantum Well and Superlatti
e Physi
s,
Pro
eedings of the SPIE 792, ed. by G. H. Dohler and J. N. S
hulman (SPIE, Washington, 1987), pp. 208.
[419 D. J. Wolford, in Pro
eedings of the 18th International Conferen
e on the Physi
s of
Semi
ondu
tors, Sto
kholm (1986), pp. 1115.
[420 E. A. Albanesi, W. R. L. Lambre
ht, and B. Segall, J. Va
. S
i. Te
hnol. B 12, 2470
(1994).
[421 S.h. Ke, K.m. Zhang, and X.d. Xie, J. Appl. Phys. 80, 2918 (1996).
[422 G. Martin, A. Bot
hkarev, A. Ro
kett, and H. Morko
, Appl. Phys. Lett.
(1996).
68,
2541
[423 J. R. Waldrop and R. W. Grant, Appl. Phys. Lett. 68, 2879 (1996).
[424 J.G. Li, Mat. Chem. Phys. 47, 126 (1997) and referen
es therein.
[425 J. P. A. Charlesworth, R. W. Godby, R. J. Needs, and L. J. Sham, Mat. S
i. Eng.
B14, 262 (1992).
218
[395 Undoped C60 is a band insulator sin
e, for example, dire
t photoemission
reates only
one hole in an otherwise lled band. This hole
an travel freely without having to pay
the large Coulomb intera
tion of U 0.5 to 1.0 eV (O. Gunnarsson, private
ommuni
ation).
[396 T. Rabenau, A. Simon, R. K. Kremer, and E. Sohmen, Z. Phys. B 90, 69 (1993).
[397 R. W. Lof, M. A. van Veenendaal, B. Koopmans, H. T. Jonkman, and G. A. Sawatzky,
Phys. Rev. Lett. 68, 3924 (1992).
[398 T. Takahashi, S. Suzuki, T. Morikawa, H. KatayamaYoshida, S. Hasegawa,
H. Inoku
hi, K. Seki, K. Kiku
hi, S. Suzuki, K. Ikemoto, and Y. A
hiba, Phys. Rev.
Lett. 68, 1232 (1992).
[399 J. H. Weaver, P. J. Benning, F. Stepniak, and D. M. Poirier, J. Phys. Chem. Solids
53, 1707 (1992).
[400 O. Gunnarsson, J. Phys.: Condens. Matter 9, 5635 (1997).
[401 X. Blase, A. Rubio, S. G. Louie, and M. L. Cohen, Europhys. Lett. 28, 335 (1994).
[402 X. Blase, A. Rubio, S. G. Louie, and M. L. Cohen, Phys. Rev. B 51, 6868 (1995).
[403 G. Bastard, Wave me
hani
s applied to semi
ondu
tor heterostru
tures (Halsted Press,
New York, 1988).
[404 J. H. Davies, The physi
s of lowdimensional semi
ondu
tors (Cambridge University
Press, Cambridge, 1998).
[405 T. P. Pearsall, StrainedLayer Superlatti
es: Physi
s, Semi
ondu
tors and Semimetals
32, edited by R. K. Williardson and A. C. Beer (A
ademi
Press, New York, 1990).
[406 M. S. Hybertsen and M. S
hluter, Phys. Rev. B 36, 9683 (1987).
[407 M. S. Hybertsen, M. S
hluter, R. People, S. A. Ja
kson, D. V. Lang, T. P. Pearsall,
J. C. Bean, J. M. Vandenberg, and J. Bevk, Phys. Rev. B 37, 10195 (1988).
[408 A. Rubio, J. L. Corkill, and M. L. Cohen, Phys. Rev. B 49, 1952 (1994).
[409 S. B. Zhang, M. S. Hybertsen, M. L. Cohen, S. G. Louie, and D. Tomanek, Phys. Rev.
Lett. 63, 1495 (1989).
[410 S. B. Zhang, M. L. Cohen, S. G. Louie, D. Tomanek, and M. S. Hybertsen, Phys. Rev.
B 41, 10058 (1990).
[411 S. B. Zhang, M. L. Cohen, and S. G. Louie, Phys. Rev. B 43, 9951 (1991).
[412 X. Zhu, S. B. Zhang, S. G. Louie, and M. L. Cohen, Phys. Rev. Lett. 63, 2112 (1989).
217
237238,
[381 F. Gygi and A. Balderes
hi, Phys. Rev. Lett. 62, 2160 (1989).
[382 V. I. Anisimov, J. Zaanen, and O. K. Andersen, Phys. Rev. B 44, 943 (1991).
[383 A. Svane and O. Gunnarsson, Phys. Rev. Lett. 65, 1148 (1990).
[384 Z. Szotek, W. M. Temmermann, and H. Winter, Phys. Rev. B 47, 4029 (1993).
[385 I. A. Drabkin, L. T. Emel'yanova, R. N. Iskenderov, and Y. M. Ksendzov, Fis. Tverd.
Tela (Leningrad) 10, 3082 (1968) [Sov. Phys. Solid State 10 2428 (1969).
[386 J. van Elp, J. L. Wieland, H. Eskes, P. Kuiper, G. A. Sawatzky, F. M. F. de Groot,
and T. S. Turner, Phys. Rev. B 44, 6090 (1991).
[387 A. Fujimori and F. Minami, Phys. Rev. B 30, 957 (1984).
[388 S. Hufner, J. Osterwalder, T. Riesterer, and F. Hulliger, Solid State Commun. 52, 793
(1984).
[389 Y. Tokura, S. Koshihara, T. Arima, H. Takagi, S. Ishibashi, T. Ido, and S. U
hida,
Phys. Rev. B 41, 11657 (1990).
[390 A. K. Cheetham and D. A. O. Hope, Phys. Rev. B
therein.
27,
[391 B. E. F. Fender, A. J. Ja
obson, and F. A. Wegwood, J. Chem. Phys. 48, 990 (1968).
[392 H. A. Alperin, J. Phys. So
. Jpn. Suppl. B 17, 12 (1962).
[393 D. Vaknin, E. Caignol, P. K. Davies, J. E. Fis
her, D. C. Johnston, and D. P. Goshorn,
Phys. Rev. B 39, 9122 (1989).
[394 S. G. Louie and E. L. Shirley, J. Phys. Chem. Solids 54, 1767 (1993).
216
39,
163
[365 S. Nakamura and G. Fasol, The blue laser diode : GaN based light emitters and lasers
(SpringerVerlag, Berlin, New York, 1997).
[366 A. F. Wright and J. S. Nelson, Phys. Rev. B 50, 2159 (1994).
[367 M. Palummo, L. Reining, R. W. Godby, C. M. Bertoni, and N. Bornsen, Europhys.
Lett. 26, 607 (1994).
[368 T. Lei, T. D. Moustakas, R. J. Graham, Y. He, and S. J. Berkowitz, J. Appl. Phys.
71, 4933 (1992); T. Lei, M. Fan
iulli, R. J. Molnar, T. D. Moustakas, R. J. Graham,
and J. S
anlon, Appl. Phys. Lett. 59, 944 (1992); C. R. Eddy, T. M. Moustakas, and
J. S
anlon, J. Appl. Phys. 73, 448 (1993).
[369 M. J. Paisley, Z. Sitar, J. B. Posthill, and R. F. Davis, J. Va
. S
i. Te
hnol. A 7, 701
(1989); Z. Sitar, M. J. Paisley, J. Ruan, J. W. Choyke, and R. F. Davis, J. Mater. S
i.
Lett. 11, 261 (1992).
[370 R. Stumpf, X. Gonze, and M. S
heer, Resear
h Report of the FritzHaber Institute,
April 1990.
[371 D. R. Hamann, M. S
hluter, and C. Chiang, Phys. Rev. Lett. 43, 1494 (1979).
[372 N. Troullier and J. L. Martins, Solid St. Commun. 74, 613 (1990).
[373 Ref. [20, p. 210.
[374 A. Os
hlies, R. W. Godby, and R. J. Needs, Phys. Rev. B 45, 13741 (1992).
[375 A. Os
hlies, R. W. Godby, and R. J. Needs, Phys. Rev. B 51, 1527 (1995).
215
[339 L. Ley, S. P. Kowal
yzk, R. A. Pollak, and D. A. Shirley, Phys. Rev. Lett 29, 1088
(1972), as presented by J. R. Chelikowsky and M. L. Cohen, Phys. Rev. B 10, 5095
(1974).
[340 W. D. Grobman and D. E. Eastman, Phys. Rev. Lett 29, 1508 (1972).
[341 M. Welkowsky and R. Braunstein, Phys. Rev. B 5, 497 (1972).
[342 J. E. Ortega and F. J. Himpsel, Phys. Rev. B 47, 2130 (1993).
[343 W. E. Spi
er and R. C. Eden, in Pro
eedings of the Ninth International Conferen
e
on the Physi
s of Semi
ondu
tors, Moskau, 1968, edited by S. M. Ryvkin (Nauka,
Leningrad, 1968), Vol. 1, p. 61.
[344 D. E. Aspnes and A. A. Studna, Solid State Commun. 11, 1375 (1972).
[345 Ref. [341 as presented by F. Szmulowi
z, Phys. Rev. B 23, 1652 (1981).
[346 R. Hulthen and N. G. Nilsson, Solid State Commun. 18, 1341 (1976).
[347 A. L. Wa
hs, T. Miller, T. C. Hsieh, A. P. Shapiro, and T.C. Chiang, Phys. Rev. B
32, 2326 (1985), as presented in Ref. [44.
[348 F. J. Himpsel, P. Heimann, and D. E. Eastman, Phys. Rev. B 24, 2003 (1981).
[349 D. Straub, L. Ley, and F. J. Himpsel, Phys. Rev. Lett. 54, 142 (1985).
[350 R. W. Godby, M. S
hluter, and L. J. Sham, Phys. Rev. B 36, 6497 (1987).
[351 D. H. Ri
h, T. Miller, G. E. Franklin, and T. C. Chiang, Phys. Rev. B 39, 1438 (1989).
[352 J. R. Chelikowsky, T. J. Wagener, J. H. Weaver, and A. Jin, Phys. Rev. B 40, 9644
(1989).
[353 E. L. Shirley, X. Zhu, and S. G. Louie, Phys. Rev. Lett. 69, 2955 (1992).
[354 Ref. [6 uses 169 plane waves whi
h
orresponds to an energy
uto of about 5.5
Hartree that is signi
antly lower than the 8.5 Hartree
uto used in the other
al
ulations.
[355 D. M. Ceperley and B. I. Alder, Phys. Rev. Lett. 45, 566 (1980).
[356 U. von Barth and L. Hedin, J. Phys. C 5, 1629 (1972).
[357 The dieren
e between relative energies in GWA and GW for the lowest dire
t band
gaps is less than 0.02 eV [102 as
an be seen in Table 21.
[358 D. Straub, L. Ley, and F. J. Himpsel, Phys. Rev. B 33, 2607 (1986).
214
[306 All realspa
e/imaginarytime 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 oset 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 shortrange Green fun
tion determines the range, not the
longrange 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 RPAbased GWA
al
ulation for simpli
ity.
[313 This so
alled \mixedspa
e" representation of the nonlo
al operators in the GWA
was introdu
ed by Godby et al. [185 and dis
ussed in detail by Blase et al. [279.
[314 A slightly dierent notation has been used in Ref. [103.
[315 H. J. Monkhorst and J. D. Pa
k, Phys. Rev. B 13, 5188 (1976).
[316 Umklapp pro
esses are negle
ted sin
e they are only important for kpoints on the
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 plasmonpole parameters,
point (v ), whi
h are not presented here.
[321 C. M. Bender and S. A. Orszag, Advan
ed Mathemati
al Methods for S
ientists and
Engineers (M
GrawHill, New York, 1978), p. 369.
[322 Note that tting s
hemes for
onvergen
e plots are not unique as dis
ussed, e.g., in
S. Wei, D. C. Allan, and J. W. Wilkins, Phys. Rev. B 46, 12411 (1992) (see Fig. 3 and
dis
ussion thereof).
212
[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
aleld fa
tor f (q ) is obtained by tting the diele
tri
onstant to quantum
MonteCarlo data [270. A similar approximation has been used by Hindgren and
Almbladh [256 who showed it to be very reliable.
[270 C. Bowen, G. Sugiyama, and B. J. Alder, Phys. Rev. B 50, 14838 (1994).
[271 This approximation ae
ts the selfenergy
orre
tions to the lowest
ondu
tion and
highest valen
e band by less than 20 meV as shown in Table 21. Also, de Groot et
al. [236 study the lowestorder vertex and self
onsisten
y
orre
tions to the RPA
polarizability and the GWA selfenergy for a 1D semi
ondu
ting wire. We will not
dis
uss that model system but
on
entrate on the results for Si.
[272 W. Kohn, Phys. Rev. 110, 857 (1958).
[273 Sili
on: "RP A = 12:8, "RP A+V +SC = 10:4, "exp = 11:4; 11:7; diamond: "RP A = 5:6,
"RP A+V +SC = 5:3, "exp = 5:5; 5:7:
[274 D. E. Aspnes and A. A. Studna, Phys. Rev. B 27, 985 (1983).
[275 W. E. Pi
kett, Comp. Phys. Rep. 9, 115 (1989).
[276 H. N. Rojas, R. W. Godby, and R. J. Needs, Phys. Rev. Lett. 74, 1827 (1995).
[277 The s
aled plasmonpole eigenve
tors for the von der Linden{Hors
h and the Engel{
Farid plasmonpole model are dened in Eqs. (63) and (72), respe
tively.
[278 L. Reining, G. Onida, and R. W. Godby, Phys. Rev. B 56, R4301 (1997).
[279 X. Blase, A. Rubio, S. G. Louie, and M. L. Cohen, Phys. Rev. B 52, R2225 (1995).
[280 A. A. Quong and A. G. Eguiluz, Phys. Rev. Lett. 70, 3955 (1993).
[281 The des
ription of bulk Si requires for example 4060 Gaussian orbitals
ompared to
about 450 plane waves [114.
[282 M. Rohlng and S. G. Louie, Phys. Rev. Lett. 80, 3320 (1998).
[283 In the
ase of bulk Si, Gaussianorbitalbased
al
ulations take as mu
h time as planewavebased
al
ulations [284. For the Si(001) (21) re
onstru
ted surfa
e a speed up
of a fa
tor of ve
ompared to plane waves is a
hieved [284.
[284 M. Rohlng, P. Kruger, and J. Pollmann, Phys. Rev. B 52, 1905 (1995).
[285 N. Hamada, M. Hwang, and A. J. Freeman, Phys. Rev. B 41, 3620 (1990).
210
[224 W. von der Linden and P. Hors
h, Phys. S
ripta 38, 617 (1988).
[225 H. J. de Groot, P. A. Bobbert, and W. van Haeringen, Phys. Rev. B 52, 11000 (1995).
[226 T. J. Pollehn, A. S
hindlmayr, and R. W. Godby, J. Phys.: Condens. Mat. 10, 1273
(1998).
[227 A. S
hindlmayr, Phys. Rev. B 56, 3528 (1997).
[228 T. M. Ri
e, Ann. Phys. 31, 100 (1965).
[229 K. W.K. Shung, B. E. Sernelius, and G. D. Mahan, Phys. Rev. B 36, 4499 (1987).
[230 W. D. S
hone and A. G. Eguiluz, Phys. Rev. Lett. 81, 1662 (1998).
[231 B. Holm and U. von Barth, Phys. Rev. B 57, 2108 (1998).
[232 E. L. Shirley, Phys. Rev. B 54, 7758 (1996).
[233 A des
ription of (multiple) satellites that improves upon the GWA
an be obtained by
umulant expansions [77 or by a Tmatrix approa
h [71. For a review, see Ref. [14.
[234 A. S
hindlmayr, T. J. Pollehn, and R. W. Godby, Phys. Rev. B 58, 12684 (1998).
[235 A. G. Eguiluz and W.D. S
hone, Mol. Phys. 94, 87 (1998).
[236 H. J. de Groot, R. T. M. Ummels, P. A. Bobbert, and W. van Haeringen, Phys. Rev.
B 54, 2374 (1996).
[237 U. von Barth and B. Holm, Phys. Rev. B 54, 8411 (1996).
[238 A. G. Eguiluz, private
ommuni
ation.
[239 B. Holm and U. von Barth, private
ommuni
ation.
[240 G. D. Mahan and B. E. Sernelius, Phys. Rev. Lett. 62, 2718 (1989).
[241 K. W.K. Shung and G. D. Mahan, Phys. Rev. Lett. 57, 1076 (1986).
[242 For a dis
ussion of the experimental value of 12.5 eV, see Se
tion 18 a.
[243 Y. Levin, C. D. Wu, and Y. BarYam, Comp. Mat. S
i. 3, 505 (1995).
[244 B. Farid, R. W. Godby, R. J. Needs, in 20th International Conferen
e on the Physi
s
of Semi
ondu
tors, edited by E. M. Anastassakis and J. D. Joannopoulos, Vol. 3, 1759
(World S
ienti
, Singapore, 1990).
[245 V. Galitskii and A. Migdal, Zh. Eksp. Teor. Fiz. 34, 139 (1958) [Sov. Phys. JETP 7,
96 (1958).
208
[183 G. Baldini and B. Bosa
hi, Phys. Stat. Solidi 38, 325 (1970).
[184 J. E. Northrup, M. S. Hybertsen, and S. G. Louie, Phys. Rev. B 39, 8198 (1989).
[185 R. W. Godby, M. S
hluter, and L. J. Sham, Phys. Rev. B 37, 10159 (1988).
[186 The dis
ontinuity of SEX equals 1.77 eV with and 2.07 eV without lo
al elds for Si.
[187 We dene semi
ore orbitals loosely as d and f orbitals that have a signi
ant overlap
with and are
lose in energy to valen
e ele
trons.
[188 G. E. Engel and R. J. Needs, Phys. Rev. B 41, 7876 (1990).
[189 V. Fiorentini, M. Methfessel, and M. S
heer, Phys. Rev. B 47, 13353 (1993).
[190 A. Nazzal and A. Qteish, Phys. Rev. B 53, 8262 (1996).
[191 S.H. Wei and A. Zunger, Phys. Rev. B 37, 8958 (1988).
[192 G. B. Ba
helet and N. E. Christensen, Phys. Rev. B 31, 879 (1985).
[193 N. E. Christensen and I. Gor
zy
a, Phys. Rev. B 50, 4397 (1994).
[194 A. Gar
ia and M. L. Cohen, Phys. Rev. B 47, 6751 (1993).
[195 W. G. Aulbur, Z. H. Levine, J. W. Wilkins, and D. C. Allan, Phys. Rev. B 51, 10691
(1995).
[196 D. Co
iorva, W. G. Aulbur, and J. W. Wilkins, unpublished.
[197 H. R. Philipp and H. Ehrenrei
h, Phys. Rev. 129, 1550 (1963).
[198 T. Tomoyse, J. Phys. So
. Jpn. 63, 1149 (1994).
[199 S. H. Wemple and M. DiDomeni
o, Jr., Phys. Rev. B 3, 1338 (1971).
[200 B. F. Levine, Phys. Rev. B 7, 2591 (1973).
[201 E. L. Shirley and R. M. Martin, Phys. Rev. B 47, 15413 (1993).
[202 W. Muller, J. Fles
h, and W. Meyer, J. Chem. Phys. 80, 3297 (1984).
[203 W. Muller and W. Meyer, J. Chem. Phys. 80, 3311 (1984).
[204 Only one planewave
al
ulation has been reported so far for ZrO2 that in
ludes the
Zr 4s, 4p, and 4d
ore and semi
ore states in addition to the 5s ele
trons as valen
e
ele
trons [57.
[205 S. G. Louie, S. Froyen, and M. L. Cohen, Phys. Rev. B 26, 1738 (1982).
206
[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 denition of the physi
ally relevant retarded diele
tri
matrix both approa
hes
are equivalent sin
e
numbers always
ommute. For the timeordered diele
tri
matrix
both approa
hes dier only in the limit ! ! 0. The formulation using the density
u
tuation operator avoids a divergen
e due to the bosoni
nature of the densitydensity
orrelation fun
tion (see, for instan
e, Refs. [18, p. 558 ., and [166).
[166 H. Stolz, Einfuhrung in die Vielelektronentheorie der Kristalle (Bertelsmann Universitatsverlag, Dusseldorf, 1975), Chapter 6.
[167 Generally, a twoparti
le Green fun
tion is dened as
^ r1 t1 ) (
^ r2 t2 )
^ y (r4t4 )
^ y(r3 t3 )jN; 0i:
G(r1 t1 ; r2 t2 ; r3 t3 ; r4 t4 ) = ( i)2 hN; 0jT [ (
[168 W. Hanke and L. J. Sham, Phys. Rev. B 21, 4656 (1980).
[169 W. Hanke, N. Meskini, and H. Weiler, in Ele
troni
Stru
ture, Dynami
s, and Quantum
Stru
tural Properties of Condensed Matter, edited by J. T. Devreese and P. Van Camp
(Plenum, New York, 1985), p. 113.
[170 H. J. Mattaus
h, W. Hanke, and G. Strinati, Phys. Rev. B 27, 3735 (1983).
[171 N. Meskini, H. J. Mattaus
h, and W. Hanke, Solid St. Commun. 48, 807 (1983).
[172 G. Strinati, H. J. Mattaus
h, and W. Hanke, Phys. Rev. Lett. 45, 290 (1980).
[173 Ex
itoni
orrelations are not in
luded in
ontrast to Ref. [156, 169.
[174 M. Albre
ht, B. Paulus, and H. Stoll, Phys. Rev. B 56, 7339 (1997).
[175 B. Paulus, P. Fulde, and H. Stoll, Phys. Rev. B 51, 10572 (1995).
[176 B. Paulus, P. Fulde, and H. Stoll, Phys. Rev. B 54, 2556 (1996).
[177 J. Grafenstein, H. Stoll, and P. Fulde, Phys. Rev. B 55, 13588 (1997).
[178 B. Paulus, private
ommuni
ation.
[179 G. Stollho and P. Fulde, Z. Phys. B 29, 231 (1978).
[180 F. Sa
hetti, J. Phys. F: Met. Phys. 12, 281 (1982).
[181 C. S. Wang and W. E. Pi
kett, Phys. Rev. Lett. 51, 597 (1983).
[182 LandoltBornstein, Numeri
al Data and Fun
tional Relationships in S
ien
e and Te
hnology, edited by K.H. Hellwege, O. Madelung, M. S
hulz, and H. Weiss, New Series,
Group III, Vol. 17 a (SpringerVerlag, New York, 1982).
205
[144 Hybertsen and Louie use a plasmonpole model, Godby and
ollaborators determine
the full frequen
y dependen
e of the s
reened intera
tion.
[145 F. Aryasetiawan and O. Gunnarsson, Phys. Rev. B 54, 17564 (1996).
[146 E. Louis, Phys. Rev. B 20, 2537 (1979).
[147 This Hamiltonian
an be derived within the framework of DFT, see Se
tion 33. The
notation in the equation is the same as used elsewhere in this arti
le.
[148 J. W. Gadzuk, Phys. Rev. B 14, 2267 (1976).
[149 C. H. Hodges, J. Phys. C: Solid St. Phys. 8, 1849 (1975).
[150 I. L. Cooper and J. Linderberg, Mole
. Phys. 25, 265 (1973).
[151 L. W. Beefermann and H. Ehrenrei
h, Phys. Rev. B 2, 364 (1970).
[152 P. Minnhagen, J. Phys. C: Solid St. Phys. 7, 3013 (1974).
[153 H. Suehiro, Y. Ousaka, and H. Yasuhara, J. Phys. C: Solid St. Phys. 17, 6685 (1984).
[154 W. Hanke and L. J. Sham, Phys. Rev. Lett. 33, 582 (1974).
[155 W. Hanke and L. J. Sham, Phys. Rev. B 12, 4501 (1974).
[156 G. Strinati, H. J. Mattaus
h, and W. Hanke, Phys. Rev. B 25, 2867 (1982).
[157 W. Borrmann and P. Fulde, Phys. Rev. B 35, 9569 (1987).
[158 S. Hors
h, P. Hors
h, and P. Fulde, Phys. Rev. B 28, 5977 (1983).
[159 S. Hors
h, P. Hors
h, and P. Fulde, Phys. Rev. B 29, 1870 (1984).
[160 W. E. Pi
kett and C. S. Wang, Phys. Rev. B 30, 4719 (1984).
[161 W. E. Pi
kett and C. S. Wang, Int. J. Quant. Chem.: Quant. Chem. Symp.
(1986).
[162 P. A. Sterne and C. S. Wang, Phys. Rev. B 37, 10436 (1988).
[163 A. B. Kunz, Phys. Rev. B 6, 606 (1972).
[164 J. Hermanson, Phys. Rev. B 6, 2427 (1972).
204
20,
299
[99 M. S
hreiber and H. Bross, J. Phys. F: Met. Phys. 13, 1895 (1983).
[100 B. I. Lundqvist, Phys. Kondens. Mater. 6, 193 (1967).
[101 B. I. Lundqvist, Phys. Kondens. Mater. 7, 117 (1968).
[102 A. Fleszar and W. Hanke, Phys. Rev. B 56, 10228 (1997).
[103 M. M. Rieger, L. Steinbe
k, I. D. White, H. N. Rojas, and R. W. Godby,
ondmat/9805246.
[104 G. Cappellini, R. Del Sole, L. Reining, and F. Be
hstedt, Phys. Rev. B 47, 9892 (1993).
[105 J. P. Walter and M. L. Cohen, Phys. Rev. B 2, 1821 (1970).
[106 Z. H. Levine and S. G. Louie, Phys. Rev. B 25, 6310 (1982).
[107 A. Balderes
hi and E. Tosatti, Phys. Rev. B 17, 4710 (1978).
[108 F. Be
hstedt, R. Del Sole, G. Cappellini, and L. Reining, Solid St. Commun. 84, 765
(1992).
[109 D. R. Penn, Phys. Rev. 128, 2093 (1962).
[110 H. Ehrenrei
h and M. H. Cohen, Phys. Rev. 115, 786 (1959).
[111 J. L. Fry, Phys. Rev. 179, 892 (1969).
[112 N. O. Lipari, J. Chem. Phys. 53, 1040 (1970).
[113 M. S. Hybertsen and S. G. Louie, Phys. Rev. B 37, 2733 (1988).
[114 M. Rohlng, P. Kruger, and J. Pollmann, Phys. Rev. B 48, 17791 (1993).
[115 N. H. Mar
h, Ele
tron Correlation in Mole
ules and Condensed Phases (Plenum Press,
New York, 1996), p. 132.
[116 D. L. Johnson, Phys. Rev. B 9, 4475 (1974); M. Taut, J. Phys. C: Solid State Physi
s
18, 2677 (1985); and Ref. [44.
[117 The use of Johnson's sum rule in
onjun
tion with nonlo
al pseudopotentials is not
justied as pointed out for instan
e in Refs. [44, 118. However, band gap errors due
to this pro
edure are only about 15 meV for Si as reported in Ref. [119.
[118 G. E. Engel and B. Farid, Phys. Rev. B 46, 15812 (1992).
[119 R. T. M. Ummels, P. A. Bobbert, W. van Haeringen, Phys. Rev. B 57 11962 (1998).
[120 G. E. Engel and B. Farid, Phys. Rev. B 47, 15931 (1993).
202
[78 S
reening ee
ts due to inhomogeneous density distributions are in this arti
le simply
alled lo
aleld ee
ts. Modi
ations of s
reening due to ex
hange and
orrelation
beyond the Hartree approximation are
alled manybody lo
aleld ee
ts.
[79 Ref. [21, Chapter 5.
[80 S. L. Adler, Phys. Rev. 126, 413 (1962).
[81 M. S. Hybertsen and S. G. Louie, Phys. Rev. B 35, 5585 (1987).
[82 N. Wiser, Phys. Rev. 129, 62 (1963).
[83 W. Brinkman and B. Goodman, Phys. Rev. 149, 597 (1966).
[84 L. Hedin, Arkiv Fysik 30, 231 (1965).
[85 J. C. Phillips, Phys. Rev. 123, 420 (1961).
[86 G. Arbman and U. von Barth, J. Phys. F 5, 1155 (1975).
[87 The determination of starting from Hartree theory requires self
onsisten
y { the
very
ompli
ation that the \best G, best W "philosophy tries to avoid { sin
e Hartree
band stru
tures and wave fun
tions for semi
ondu
tors and insulators are qualitatively
wrong [88, 89.
[88 R. Daling and W. van Haeringen, Phys. Rev. B 40, 11659 (1989).
[89 R. Del Sole, L. Reining, and R. W. Godby, Phys. Rev. B 49, 8024 (1994).
[90 F. Gygi and A. Balderes
hi, Phys. Rev. B 34, 4405 (1986).
[91 S. Massidda, A. Continenza, M. Posternak, and A. Balderes
hi, Phys. Rev. Lett. 74,
2323 (1995).
[92 J. P. Walter and M. L. Cohen, Phys. Rev. B 5, 3101 (1972).
[93 A. Overhauser, Phys. Rev. B 3, 1888 (1971).
[94 Ref. [19, p. 56/57.
[95 There are simplied tightbinding models that sum all dipole
ontributions to get an
ee
tive s
reening potential that depends only on the lo
al ele
tron density, see, for
instan
e, Refs. [96 and [97.
[96 W. Hanke and L. J. Sham, Phys. Rev. B 38, 13361 (1988).
[97 P. A. Sterne and J. C. Inkson, J. Phys. C: Solid State Phys. 17, 1497 (1984).
[98 B. I. Lundqvist, Phys. Kondens. Mater. 6, 206 (1967).
201
[59 See Se
tions 7, 11, and 30 for further dis
ussions of this point.
[60 Se
tions 4 and 5 follow Ref. [4
losely. However, we do not
onsider the spin degrees
of freedom expli
itly.
[61 We add innitesimal
onvergen
e fa
tors i to Ei for Ei <> .
[62 G. Baym and L. Kadano, Phys. Rev. 124, 287 (1961).
[63 G. Baym, Phys. Rev. 127, 1391 (1962).
[64 Both names are used inter
hangeably in the literature. We will use the name \energydependent
orrelation
ontribution" for the W v
ontribution to the selfenergy
throughout this arti
le.
[65 U. von Barth and L. Hedin, Nuovo Cimento 23B, 1 (1974).
[66 G. Wendin, Breakdown of the OneEle
tron Pi
tures in Photoele
tron Spe
tra (Springer,
Berlin, 1981), p. 24.
[67 E. L. Shirley and R. M. Martin, Phys. Rev. B 47, 15404 (1993).
[68 F. Aryasetiawan, Phys. Rev. B 46, 13051 (1992).
[69 F. Aryasetiawan and U. von Barth, Phys. S
ripta T45, 270 (1992).
[70 A. Liebs
h, Phys. Rev. B 23, 5203 (1981).
[71 M. Springer, F. Aryasetiawan, and K. Karlsson, Phys. Rev. Lett. 80, 2389 (1998), and
referen
es therein.
[72 L. Hedin, B. I. Lundqvist, and S. Lundqvist, J. Res. Natl. Bur. Stand. Se
t. A 74A,
417 (1970).
[73 L. Hedin, Physi
a S
ripta 21, 477 (1980).
[74 D. C. Langreth, Phys. Rev. B 1, 471 (1970).
[75 P. Minnhagen, J. Phys. C: Solid St. Phys. 8, 1535 (1975).
[76 The term shakeup spe
tra
orresponds to ex
itations whi
h are
reated by a sudden
hange in a quantum me
hani
al system. Consider, for example, the
reation of a
ore
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 shakeup and shakeo pro
esses.
[77 F. Aryasetiawan, L. Hedin, and K. Karlsson, Phys. Rev. Lett. 77, 2268 (1996).
200
[38 Theory of the inhomogeneous ele
tron gas, edited by S. Lundqvist and N. H. Mar
h
(Plenum Press, New York and London, 1983).
[39 L. J. Sham and W. Kohn, Phys. Rev. 145, 561 (1966).
[40 J. P. Perdew, R. G. Parr, M. Levy, and J. L. Balduz, Phys. Rev. Lett. 49, 1691 (1982).
[41 For a more detailed des
ription see Appendix A.
[42 W. G. Aulbur and J. W. Wilkins, unpublished.
[43 E. L. Shirley, X. Zhu, and S. G. Louie, Phys. Rev. B 56, 6648 (1997).
[44 M. S. Hybertsen and S. G. Louie, Phys. Rev. B 34, 5390 (1986).
[45 J. L. Corkill and M. L. Cohen, Phys. Rev. B 48, 17622 (1993).
[46 M. P. Surh, S. G. Louie, and M. L. Cohen, Phys. Rev. B 43, 9126 (1991).
[47 A. Rubio, J. L. Corkill, M. L. Cohen, E. L. Shirley, and S. G. Louie, Phys. Rev. B 48,
11810 (1993).
[48 X. Zhu and S. G. Louie, Phys. Rev. B 43, 14142 (1991).
[49 A. Rubio and M. L. Cohen, Phys. Rev. B 51, 4343 (1995).
[50 S. Massidda, R. Resta, M. Posternak, and A. Balderes
hi, Phys. Rev. B
(1995).
52,
R16977
50,
[52 M. Rohlng, P. Kruger, and J. Pollmann, Phys. Rev. Lett. 75, 3489 (1995).
[53 U. S
honberger and F. Aryasetiawan, Phys. Rev. B 52, 8788 (1995).
[54 S. Massidda, A. Continenza, M. Posternak, and A. Balderes
hi, Phys. Rev. B
13494 (1997).
55,
[55 F. Aryasetiawan and O. Gunnarsson, Phys. Rev. Lett. 74, 3221 (1995).
[56 S. Albre
ht, G. Onida, and L. Reining, Phys. Rev. B 55, 10278 (1997).
[57 B. Kralik, E. K. Chang, and S. G. Louie, Phys. Rev. B 57, 7027 (1998).
[58 M. Palummo, L. Reining, M. Meyer, and C. M. Bertoni, 22nd International Conferen
e
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 manyparti
le systems (M
GrawHill, New York, 1971).
[19 P. Fulde, Ele
tron Correlations in Mole
ules and Solids, Springer Series in SolidState
S
ien
es 100, Chapter 9 (Springer Verlag, Berlin, 1991).
[20 J. C. Inkson, Manybody theory of solids (Plenum Press, New York, 1984).
[21 G. D. Mahan, ManyParti
le Physi
s (Plenum Press, New York, 1993), 2nd edition.
[22 R. D. Mattu
k, A Guide to Feynman Diagrams in the ManyBody 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).
[28 S. Hufner, Photoele
tron Spe
tros
opy, Springer Series in SolidState S
ien
es (Springer
Verlag, Berlin, 1996).
[29 J. Fraxedas, M. K. Kelly, and M. Cardona, Phys. Rev. B 43, 2159 (1991).
[30 N. V. Smith, P. Thiry, and Y. Petro, Phys. Rev. B 47, 15476 (1993).
[31 Other independentparti
le Hamiltonians su
h as Hartree, HartreeFo
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 KohnSham 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 selfenergy 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,
ed. by
69,
ed.
196
Figure 49: Ee
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; longdashed line { selfenergy
orre
ted without quasiparti
leweight
orre
tion; dashdotted { selfenergy
orre
ted
with weight fa
tor Z
Zv for ea
h matrix element; solid line { selfenergy
orre
ted in
luding
vertex
orre
tions. The
lose agreement between the solid and longdashed
urve shows that
the strong ee
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 (fullpotential 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 ee
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 selfenergy (i) is virtually identi
al to Vx
LDA in the
Alregion, 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
estate 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 selfenergy 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 energydependent quasiparti
le
equation. Figure taken from Ref. [499.
192
Figure 44: The absolute value of the quasiparti
le energies of the highesto
upied (left)
and lowestuno
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 totalenergy dieren
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 highesto
upied states in
ontrast to
LDA. The same is true for the lowestuno
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 selfenergy
and are represented by solid
urves. The QP bands are narrower than the nearlyfreeele
tron
bands (NFE, dashed
urves) by 0.37 eV. The full theory (solid dots) also in
ludes surfa
e
ee
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: Selfenergy of a 5s photoele
tron in Ag relative to the Fermi energy as a fun
tion of
energy. The dierent
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 ee
ts
of a nite imaginary part of the selfenergy (dashdotted 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 selfenergy qualitatively. S
reening and a nonzero imaginary part
of the selfenergy ae
t the results quantitatively. Figure taken from Ref. [216.
189
Figure 41: Selfenergy
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 dierent values of the
angular momentum l (dashed lines). Comparison of the sum of the s, p, and d
ontributions
(dasheddotted line) with the solution that takes the ee
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
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, HartreeFo
k (HF), and GWA (Ref. [67) and from the lo
al spin density approximation (LSDA) and from the s
reenedex
hange lo
al spin density approximation (LSDSX) [486 from Ref. [485. GWA improves upon HartreeFo
k for all elements and upon
the lo
al spindensity 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
tronhole attra
tion in the Hamiltonian, the longdashed line in
ludes
only lo
al elds, and the shortdashed line only RPA s
reening with quasiparti
le shifts.
The lowenergy 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
tronhole intera
tion (dashed lines), and experimental
results from Ref. [142, 478 (solid lines). The right panel
ontains theoreti
al results in
luding
the ele
tronhole intera
tion (dashed line) and the same experimental results (solid line).
Ex
itoni
ee
ts improve agreement between theory and experiment signi
antly for peak
position and height and are larger in largegap 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 HartreeFo
k (HF), GWA (GW),
and LDA. GWA is
lose to HartreeFo
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
estate 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 angleresolved 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
Figure 34: S
hemati
representation of the volumeaveraged dipole density n(z ) (dashed
line), the Hartree potential V (z ) (solid line), and the interfa
e
ondu
tionband oset, E
,
and valen
eband oset, 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 dieren
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 selfenergy
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 dieren
e between the selfenergy
orre
tions in the superlatti
e and
the bulk materials is found sin
e selfenergy ee
ts in Si and Ge are very
lose. All values
are aligned with respe
t to the valen
eband edge. Figure taken from Ref. [406.
180
15
Si
GW
LDA
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
PE0
PE1
PE2
MPI_GATHER
fourth block of r vectors
PE3
Figure 30: Communi
ation stru
ture for the redistribution of the independentparti
le polarizability over PEs. After the rst 3D FFT ea
h PE has the independentparti
le polarizability P 0 (k; r; G0; i ) for one parti
ular kpoint, a subset of rve
tors in the irredu
ible
realspa
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 rve
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 dierent length of the rblo
ks in the pi
ture
orresponds to a dierent number of rpoints 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
PEi
PE0
Disk
PE0
Disk
PE1
PE2
0
calculate G (r, r, +it)
0
write P (r , r, +it) to disk
PEi
PE0
Disk
0
distribute P (r , r, +it)
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)
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 realspa
e GWA
ode. We list all
ommuni
ation and
al
ulational steps needed to
determine the independentparti
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
PEi
PE0
Disk
PE0
Disk
PE1
PE2
calculate
i
vc
vc
M G (k,q)[MG(k,q)]*
(k,q) =
c v
GG
v,kq  c,k
i
P
PE1
singlenode 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 independentparti
le polarizability in re
ipro
al spa
e [Eq. (123). The same s
heme applies to the
al
ulation of
the selfenergy 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 independentparti
le polarizability. The partial
ontributions are summed up at the end of the
al
ulation via a singlenode a
umulation
on PE0.
176
1
Si
25v=0.0
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
uto of 8.5 Hartree is about 310. The sum over re
ipro
al Gve
tors is
uto at 2.7
Hartree. All other numeri
al parameters are identi
al to those in Table 18.
175
1
Si
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 Gve
tors is
uto at 2.7 Hartree. All other numeri
al parameters are identi
al
to those in Table 18.
174
Si
25v=0.0
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 Gve
tors in the internal sum over Gve
tors in Eq. (106).
Convergen
e is smooth and about 100 Gve
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 Gve
tors
orresponding
to a
uto 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
2
3
4
1v
15c
2c
3
4
5
6
20
40
number of kpoints 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 kpoints used in the integration of the selfenergy [Eqs. (117) and
(118). Convergen
e is smooth with the equivalent of 10 kpoints in the IBZ being ne
essary
to
onverge the lowlying 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
utos are given in Table 18.
172
Im
Re
2
Im
10
Re
20
10
60
40
20
0
20
(eV)
40
60
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. Lowestorder 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 . SC1SC4 denote
orre
tions due to selfenergy insertions in the Green fun
tion,
i.e., due to lowestorder self
onsisten
y ee
ts. V
orresponds to a ladder diagram whi
h is
the lowestorder vertex
orre
tion. The solid dire
ted line denotes the LDA Green fun
tion.
The
ross denotes Vx
and the wiggly line denotes the RPAdynami
allys
reened intera
tion. Right panel: GWA selfenergy plus lowestorder self
onsisten
y (SC1SC4) and vertex
(V)
orre
tions. The diagrams SC3 and SC4 are selfenergy
orre
tions due to lowestorder
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 independentparti
le band width vs. ele
tron
density parameter rs for the homogeneous ele
tron gas and several approa
hes to the determination of the selfenergy. 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 selfenergy ) 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 manybody lo
aleld fa
tor [264. This
urve is universal in the sense that
it is hardly ae
ted by a
hange of the manybody lo
aleld 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 selfenergy
an
els the ee
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 nonintera
ting ele
trons (dasheddotted line). Only the standard
G0 W0 A
al
ulation leads to bandwidth narrowing in
omparison to the freeele
tron result. However, this observed bandwidth 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
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 oneparti
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 dier 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 selfenergy with respe
t
to LDA orbitals
al
ulated at the energy of the
orresponding quasiparti
le peak. The
shape of the imaginary Si selfenergy is similar to the shape of the nonself
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 (timedependent) LDA vertex fun
tion
in
luded (GW
al
ulation, see Se
tion 14). The selfenergy 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 kpoints
(k) (eV)
1.5
1.0
0.5
4
5
6
Wave Vector
10
Figure 14: Selfenergy
orre
tion (k) = h(E ) Vx
LDA i to the dire
t band gap at the
x
point and at 10 spe
ial
kpoints in the f
Brillouin zone for Si, SiC, and GaN. The standard
deviation from the average selfenergy
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 selfenergy
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 selfenergy 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 selfenergy 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 stateindependent and amounts to about 0.2. This indi
ates, that
dynami
al ee
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 selfenergy 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 dieren
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 selfenergy 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 bareex
hange (HartreeFo
k) selfenergy operator of Si hX i
and the stati
ally s
reened ex
hange selfenergy operator hSSX i. hVx
LDAi is subtra
ted as
in (b). The nonlo
ality of X has too large a range due to the negle
t of s
reening whi
h
leads to a jump in the selfenergy
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 selfenergy h (! = midgap)=! i. Figure taken from
Ref. [185.
160
Figure 11: Contour plots of the selfenergy (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 selfenergy 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 nonlo
ality of the selfenergy (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
aleld (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 shortranged and be
ome negligible after one bond length. Figure adapted from
Ref. [44.
158
Figure 9: Plot of the selfenergy (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 highestlying valen
e (lowestlying
ondu
tion) band wave fun
tion
lose to the point
al
ulated in the LDA. The range of nonlo
ality of the selfenergy 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 nonlo
ality of the selfenergy and the nodal stru
ture of the
ondu
tion band wave
fun
tion. Hen
e, the selfenergy 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 LevineLouie model
diele
tri
fun
tion (dashed line) [106. RPA results by Balderes
hi and Tosatti (stars) [107
for large q seem to favor the LevineLouie 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
tronhole intera
tion in the timedependent HartreeFo
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 innite sum of ladder diagrams whereas the
se
ond term generates an innite sum of polarization bubbles (
ompare Eq. (77)). Taken
from Ref. [168.
156
0.5*[(k F +q)2k 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
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 singleparti
le ex
itations is
0:5[(kF + q )2 kF2 (0:5[( kF + q )2 kF2 ). In simple plasmonpole 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 plasmonpole 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
alpseudopotentialbased results by Walter and Cohen [92 in
omparison to the HybertsenLouie plasmonpole
model. The average behavior of the inverse diele
tri
fun
tion is
aptured rather well by the
plasmonpole 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
153
2
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 rstprin
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 modelGWA
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
ee
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
photoelectron spectroscopy
inverse photoemission
E gap
h
VB
photoelectron
inverse
spectroscopy
photoemission
N > N  1
N > N + 1
151
A(E)
noninteracting
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 manybody system. The dieren
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 innite life time of the nonintera
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
EXXKS 3.3 /2.9b
EXX+x
9.6a
KLIKS
2.9
sXLDA
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 { Diusion MC, i Ref. [613 { Variational MC.
Table 39: Dire
t band gaps in eV at for densityfun
tional methods that go beyond LDA
ompared to experiment, GWA and HartreeFo
k: EXXKS { KohnSham orbital gap with
exa
t ex
hange; EXX+x { full band gap with exa
t ex
hange in
luding the gap dis
ontinuity x ; KLIKS { KohnSham gap with the simplied exa
tex
hange method of Krieger, Li,
and Iafrate; sXLDA { generalized nonlo
al KohnSham formulation with s
reened ex
hange
and lo
aldensity approximation of
orrelation; Frits
he { Frits
he's generalized density fun
tional theory for ex
ited states; QMC { quantum Monte Carlo bandstru
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 HartreeFo
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.
Table 38: Lo
aleld (LF)
orre
tions for selenium and quartz (SiO2) in diele
tri
onstant
, se
ondharmoni
oe
ient d, and opti
al rotatory power [543, 583. Modest lo
aleld
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
aleld
orre
tion diers between Se and quartz.
For the se
ondharmoni
oe
ient d, there are more experimental results than quoted in
the table. For selenium these experimental values vary substantially, while for quartz the
dierent 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 zerofrequen
y
limits given in Ref. [583, whi
h were extrapolated from the data of Refs. [584, 585 (Se) and
Ref. [586 (quartz).
148
Table 36: Diele
tri
onstants for largegap insulators in LDA and within the s
issorsshift
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 GWAbased s
issorsshift 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
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 dierent 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
orepolarization ee
ts. The
rst
olumn is the LDA gap error given by the dieren
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.
Table 35: Diele
tri
onstants for small and mediumgap semi
ondu
tors in LDA and within
the s
issorsshift approa
h without (No LF) and with (LF) lo
aleld
orre
tions [536, 541.
The values in
luding lo
aleld
orre
tions are all within 5% of experiment.
146
NR
Si
2.7a;b
Ge
0.7a;b
GaAs 1.1a;b
SRPP
2.6
;d
0.0g
0.6d;g;h;i
Egap (eV)
FRPP
FRCR
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 dierent 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 dierent referen
es.
145
rs
Al
Li
Na
K
2.1
3.3
4.0
4.9
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 selfenergy [232, and (iii) nonzero imaginary part
of and surfa
e ee
ts [229, 265. Agreement with experiment is generally good. However,
self
onsisten
y ee
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 nearlyfreeele
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
WignerSeitz 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 sppromotion energies in GWA, HartreeFo
k (HF), lo
al spin density fun
tional theory (LSDA), and experiment for the groupIII
elements boron, aluminum, and gallium. GWA improves upon HartreeFo
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 oset in eV at the nonpolar, 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 selfenergy
orre
tion
of 0.25 eV equals about 30% of the LDA valen
e band oset 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.
kpoint
K
M
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 selfintera
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
3.84.2
;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 transitionmetal oxides obtained
in abinitio 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 selfintera
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
dierent
al
ulations of the LDA and GWA energies for both the valen
e band maximum
and
ondu
tion band minimum dier 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 pseudopotentialplanewave 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 dieren
es in the data. Further deviations may result from
the dierent
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 Rohlng [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 highsymmetry 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 Gaussianorbitalbased
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 ee
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. Spinorbit splitting is negle
ted
in the experimental data. Most of the experimental data are at room temperature.
Ref.
Aulbur [42
Rohlng [114
Ba
kes [130
Aulbur [42
Rohlng [114
Ba
kes [130
Aulbur [42
Rohlng [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
dieren
es between the dierent
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
planewave
al
ulations [42, 130 and of a Gaussianorbital 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
Rohlng [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
Rohlng [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
Rohlng [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
Rohlng [114
Hybertsen [44
Shirley [43
12.74
12.79
X1v
9.3(2)b
Expt.a
Aulbur [42
Rohlng [114
Hybertsen [44
Shirley [43
Expt.a
Aulbur [42
Rohlng [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
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
tionband energies vary by 0.1 to 1.6 eV between dierent
al
ulations due to a dierent treatment of
orevalen
e polarization and of
ore relaxation, a
use of updated quasiparti
le energies rather than LDA energies in the Green fun
tion, and
dierent degrees of
onvergen
e (see Table 15). All
al
ulations use plasmonpole models.
The
hosen basis set is plane waves ex
ept for the Gaussian orbital
al
ulation by Rohlng
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
orepolarization potentials whi
h are ne
essary to determine the quasiparti
le gap in quantitative agreement with experiment. Hybertsen and Louie in
lude spinorbit (SO)
oupling
to rst order. All energies are in eV.
135
Table 21: Comparison of Si LDA (roman), GWA (boldfa
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 dierent
al
ulations for both
ondu
tion and valen
eband states
vary between 0.1 and 0.6 eV due to dierent te
hniques, dierent 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 plasmonpole model (PPM),
and determine selfenergy shifts in rstorder perturbation theory (PT). Cal
ulations that
do not use a plasmonpole 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
ebandwidth de
rease of
about 0.3 eV but ae
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 ee
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
Rohlng [114
Hamada [285
Hybertsen
[5, 44
Godby [6
Rieger [103
Fleszar [102
Expt.
Aulbur [42
Rohlng [114
Hamada [285
Hybertsen
[5, 44
Godby [6
Rieger [103
Fleszar [102
Expt.
Aulbur [42
Rohlng [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
3.343.36,
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 TroullierMartins [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 lowlying
ondu
tion band state to
onverge. The
hoi
e
of the pseudopotential ae
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) plasmonpole models for highsymmetry 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
lowlying 1v state, for whi
h the plasmonpole 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 dieren
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
Table 18: Parameters used to determine the self
onsistent density n(r), the independentparti
le polarizability P 0 [
f. Eq. (116), and the selfenergy [
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 plasmonpole model and the Gygi{Balderes
hi s
heme for the
integration of the Coulomb singularity are used. For the latter s
heme, the plasmonpole
band stru
ture is determined at q = 0:00125qX using the equivalent of 60 spe
ial kpoints
in the irredu
ible Brillouin zone. Troullier{Martins pseudopotentials with nonlinear
ore
orre
tions for GaAs and GaN are used to model the ioni
potential. The energy
uto
E
ut is in Hartree, the
uto 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 kpoints in the irredu
ible Brillouin
zone obtained using the full spa
egroup symmetry of the
rystal and Nppm is the number of
plasmonpole 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
uto used to determine the self
onsistent groundstate density as
well as the wave fun
tions used to
al
ulate the independentparti
le polarizability and the
expe
tation values of the selfenergy operator. Deviations between the dierent eigenvalues
are less than 0.08 eV. All
al
ulational parameters are given in Table 18 ex
ept for the
uto
in re
ipro
al spa
e for the determination of whi
h is 2.7 a.u. for the present study. The
uto energy E
ut is given in Hartree.
129
1.60
valen e
0.84
Exp.a
a
Egap (eV)
Zakharov
Rohlng 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 Rohlng
5.05
5.05
( 13.2%) ( 13.2%)
5.33
( 8.4%)
5.78
5.61
( 0.7%) ( 3.6%)
5.818
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
alarrelativisti
TroullierMartins 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
alarrelativisti
Ba
heletHamannS
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
ee
ts (numbers in parentheses) in
reases fundamental
band gaps by about 0.3 eV. Zakharov et al. [51 use semirelativisti
, nonlo
al pseudopotentials with nonlinear
ore
orre
tions (NLCC) [205 (E
ut = 12.5 Hartree). Rohlng et
al. [52 and Fleszar [302 use s
alarrelativisti
Ba
heletHamannS
hluter pseudopotentials.
The dieren
e of about 0.5 eV in the fundamental LDA band gap between dierent Cd2+
al
ulations is of the same order as the GWA bandgap 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 dieren
e in the equilibrium stru
ture leads to dieren
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 Gaussianorbitalbased method [114, 295 in
omparison to a planewave (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 40Gaussian 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 mediumgap 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
selfenergy/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 lowestorder vertex (V) and self
onsisten
y (SC)
orre
tions to the
selfenergy (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. Lowestorder
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). Lowestorder
orre
tions to the selfenergy 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 ee
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 selfenergy ),
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 selfenergy does not have a signi
ant ee
t on relative energy dieren
es
ompared
to RPAbased 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 nonself
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 selfenergy (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 plasmonpole 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 ee
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 SIRCPSP;
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
eband
maximum. The experimental data are weighted averages of spinorbitsplit 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 Slatertransitionstate (STS) results obtained by an LMTO
al
ulation [145. For CdS,
we list the LDA and selfintera
tion and relaxation
orre
ted pseudopotential (SIRCPSP)
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 dieren
es in Ge and GaAs in eV. Results for LDA fullpotential
al
ulations, quasiparti
le (QP)
al
ulations with an LDA treatment of
orevalen
e intera
tions
(CVI), quasiparti
le
al
ulations with a
orepolarizationpotentialbased (CPP) treatment
of
orevalen
e intera
tions, and experiment are shown. All results in
lude
orerelaxation
ee
ts (added a posteriori for the quasiparti
le
al
ulations). Fundamental band gaps in the
dierent approa
hes are printed in bold fa
e. Overall agreement between experiment and
quasiparti
le
al
ulations is improved upon in
lusion of
orepolarization ee
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
kpoint
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
kpoint
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 spbonded materials shown in the table, Zi is equal
to 0.8 to within 10% and therefore approximately a material and stateindependent
onstant. Note, however, that
ovalentlybonded 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
ebandmaximum and
ondu
tionbandminimum selfenergies with and without lo
al elds for Si in
omparison
to the GWA selfenergy. Lo
aleld ee
ts ae
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 selfenergies
upwards by about 10 to 20%. In absolute terms and for the total selfenergy, 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
Table 8: Range rnlo
of the selfenergy 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 selfenergy 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 selfenergy 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
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 HartreeFo
k
al
ulations using the single
meanvalue 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 HartreeFo
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.
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 bandgap in
rease and to an overestimation of experiment by about 0.4 to 1.1 eV.
Dynami
ee
ts (GWA) redu
e this overestimation and reprodu
e experiment to within 0.1
to 0.3 eV. Note, that relativisti
ee
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
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 dierent
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
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
Denition
(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
singleparti
le energy
N ele
tron total energy for state i
ith quasiparti
le energy
ith quasihole energy
wave fun
tion of singleparti
le Hamiltonian
ith ex
ited (i=0 ground) state of N ele
tron system
quasiparti
le manybody amplitude
quasihole manybody amplitude
singleparti
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
nonHermitian, nonlo
al, energydependent selfenergy
= ex
hange + energydependent
orrelation selfenergy
= Coulomb hole + s
reened ex
hange selfenergy
vertex fun
tion
u
tuation potential
energy of ele
tronhole ex
itation
Table 1: Denitions 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
KohnSham 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 ee
t of the
oupling
onstant average is to in
orporate the dieren
e between T0 and the total physi
al
kineti
energy into the KohnSham ex
hange
orrelation fun
tional Ex
. The KohnSham
onstru
tion is made spe
i
ally to obtain a set of singleparti
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 KohnSham 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 dene an ex
hange
orrelation energy per ele
tron Ux
(r) by:
Ex [n =
(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 KohnSham theory. Even earlier, the rst de fa
to density fun
tional
theory was the ThomasFermi equation in whi
h the kineti
energy is also treated in a lo
al
approximation [667, 668.
The lo
aldensity approximation is by
onstru
tion exa
t for homogeneous systems, and
is the zerothorder 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
orrelationhole
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
fulll. 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
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 nonzero
omponents and
the pairdistribution fun
tion is a twobytwo matrix in the spin indi
es. The sum rule in
Eq. (177) is then modied to
Z
(178)
(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 pairdistribution 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 ee
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 ee
ts only ex
hange. The sum rule
for g des
ribes the important role of ex
hange to subtra
t out the selfintera
tion pie
e from
the Hartree term, whi
h pie
e has been unphysi
ally in
luded in the Hartree term when
dened in terms of an integral over the total densities. For spin onehalf ele
trons g "" des
ribes both ex
hange and Coulomb
orrelation among the equalspin 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 dieren
e
between the KohnSham 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 innitesimally, while the dis
ontinuity in the
kineti
energy T0 is exa
tly equal to the KohnSham gap "N;N +1 "N;N . This dis
ontinuity
in the kineti
energy is due to the qualitative dieren
e between the lowest
ondu
tionband orbital and the highest valen
eband orbital. However, the denition 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
tionband orbital in the (N +1)ele
tron system and the highest
valen
eband orbital in the N ele
tron system [662.
Numeri
al implementations of KohnSham theory, using LDA or GGA (see Se
tion f.
of this appendix), typi
ally obtain KohnSham 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 KohnSham theory to give band gaps
lose to experiment is often
refered to as the `bandgap problem' and is the main reason why quasiparti
le
al
ulations
are needed as a
omplement to KohnSham 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 dene the density
n(r) by
Z
(174)
n(r) = N j (r; r2; : : : ; rN )j2 dr2 : : : 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 dened
through
n(r; r0 ) = n(r)n(r0 )(1 + g (r; r0)):
(176)
If we put g = 0, the pairdistribution 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
(177)
In systems with a fra
tional number of ele
trons, the KohnSham 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 KohnSham 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 , innitesimal. That is, by the
hemi
al potential for integer N we here
mean, by denition, the
hemi
al potential of a system with a fra
tional o
upation of the
N th KohnSham orbital. The notation "N;M refers to the energy of the M th KohnSham
orbital in the N ele
tron system.
. The bandgap dis
ontinuity
Let us rst dene 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 groundstate 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:
(171)
The quasiparti le band gap Egap is given by the dieren e between I and A:
Egap = I
A = "N +1;N +1
"N;N = x + "N;N +1
"N;N ;
(172)
where we have dened x
= "N +1;N +1 "N;N +1 , that is, the energy dieren
e between
the highest o
upied KohnSham orbital in the (N +1)ele
tron system and the lowest uno
upied KohnSham orbital in the N ele
tron system. This dieren
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 KohnSham
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 dieren
e between the ex
hange
orrelation
potentials in the (N +1)ele
tron system and the N ele
tron system is a positionindependent
110
Formally, the KohnSham potential
an be obtained from the fun
tional F [n. The rst
step is to dene 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 totalenergy fun
tional of the KohnSham system is
EKS [n = T0 [n +
(161)
When the minimization in Eq. (160) is extended to in
lude mixed states and fra
tional
o
upation, T0 [n has a welldened 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 dened 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
n(r)n(r0 )
jr
r0
(163)
0
j drdr
(164)
F [n T0 [n = EH [n + Ex [n:
(165)
(EH [n + Ex
[n)
VKS =
+ Vext = VH + Vx
+ Vext ;
n
n=n0
(166)
VH (r) =
n0 (r0 ) 0
0 dr
jr
(167)
E [n
Vx
(r) = x
n(r) n=n0
109
(168)
When a fra
tional total number of ele
trons is allowed, the Rgroundstate 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)
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 singleparti
le potential that is an
impli
it fun
tional of the exa
t groundstate density n0 . The KohnSham equations must be
solved self
onsistently so that both equations in Eq. (159) are fullled.
108
(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 diers 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 dene 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 +
(156)
The above formulation is valid for an integer number of ele
trons. However, the denition of
the fun
tionals
an be extended to noninteger ele
tron numbers by the in
lusion of mixtures
between states with dierent 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
106
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 timedependent densityfun
tional theory
with a stati
LDA kernel to des
ribe the ee
t of ex
hange and
orrelation on the lo
al
elds. The need for a s
issorsoperator
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 timedependent 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 imaginarytime
S
hrodinger equation by numeri
ally simulated diusion { diusion [643 or Green fun
tion Monte Carlo [644. In both these methods, a realspa
e manyele
tron wave fun
tion
representation allows the generation of highly a
urate wave fun
tions, in
luding strong
orrelation ee
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 diusion Monte Carlo, the mathemati
al equivalen
e between
the imaginarytime S
hrodinger equation and a realtime diusion equation is used to propagate the S
hrodinger equation by simulated numeri
al diusion of a
olle
tion of
titious
parti
les (\walkers") whose density
orresponds to the wave fun
tion. Propagation of the
imaginarytime 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, diusion Monte Carlo
al
ulation.
Appli
ation of diusion 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 `xednode'
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 singleparti
le orbitals obtained from,
104
with some ex
itedstate orbitals o
upied. This Slater determinant is identied 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 equalspin 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 oppositespin
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. TIMEDEPENDENT DENSITY FUNCTIONAL THEORY
For nite systems, a pra
ti
al method for obtaining ex
itedstate energies is to nd the
poles in the frequen
ydependent linearresponse fun
tions [629. Within densityfun
tional
theory this approa
h requires an extension of KohnSham theory to timedependent 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 timedependent density fun
tional
theory see, for example, Ref. [631.
As for the timeindependent
ase, the ex
hange and
orrelation ee
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 lowfrequen
ies and for slowly varying densities is given by the adiabati
lo
aldensity
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
aldensity 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
satised by nonlo
al kernels. A
entral issue in timedependent 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
aldensity kernel of Gross and Kohn [635, whi
h violates
the harmoni
potential
onstraints, and exa
tex
hange kernels [636, 637. The
oupling
onstant perturbation theory of Gorling
an also be extended to timedependent 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 densitypolarization 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
itedstate
onguration 2s2 yields an extremum of E [n while the
onguration 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 groundstate
fun
tional, so no pra
ti
al approa
h is obtained from these
onsiderations.
Theophilou and
ollaborators [622, 623 demonstrate that ex
itedstate energies
an be
obtained from an extension of density fun
tional theory to the sum of the lowestlying states.
For the ground state, the RayleighRitz variational prin
iple states that the groundstate
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 HohenbergKohn 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
itedstate energy of a given state
an be found with this extended formulation if
the energies of all the lowerlying states are known. For example, to obtain the energy of
the rst ex
ited state, the groundstate energy is rst
al
ulated and then the sum of the
groundstate and the ex
itedstate energies. From these two
al
ulations, the ex
itedstate
energy is obtained by subtra
tion. This so
alled ensemble densityfun
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 dierent 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
itedstate 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 HohenbergKohn 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 KohnSham 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
itedstate 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 KohnSham 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
itedstate density of a given ex
ited state in the intera
ting system. The
KohnSham potential in this formalism is therefore dierent for ea
h ex
ited state, and the
nonintera
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 KohnSham and the intera
ting system, but also between
all the ex
ited states of the two systems. Perturbation theory to innite order in the
oupling
onstant then gives all the ex
itedstate properties of the intera
ting system as fun
tions of
the
omplete set of KohnSham orbitals and energies, in
luding the orbitals uno
upied in
the ground state. These orbitals and energies are all determined by the KohnSham potential
and are in that sense fun
tionals of the exa
t groundstate density, sin
e the KohnSham
potential is uniquely determined by the groundstate density.
In the KohnSham system, the ex
ited states are given by all possible Slater determinants that
an be formed from the
omplete set of singleparti
le KohnSham orbitals. By
onstru
tion, the groundstate determinant yields the
orre
t groundstate density, while the
ex
ited KohnSham determinants yield densities and energies that are not equal to the exa
t
ex
itedstate energies and densities. However, by the assumed adiabati
onne
tion between
the KohnSham and the intera
ting system, the exa
t energies and densities are obtained as
an innite perturbation series in the
oupling
onstant. For example, in the
oupling
onstant expansion of the band gap the zerothorder term is the KohnSham gap, the rstorder
orre
tion is the ex
hange
ontribution, and the higherorder 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 EXCITEDSTATE DENSITIES
In Appendix A, the universal fun
tional F [n that appears in the HohenbergKohn theory
as rened by Levy [618, 619 and Lieb [620 is dened 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 dened for a very large set of densities, and in parti
ular for any
wellbehaved ex
itedstate 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 groundstate
onguration 1s2 , the
101
T0 [n = min
hjT^ji:
!n
(149)
To in
lude ex
hange, Seidl et al. dene 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
(150)
Ex [fi g =
jr
i<j
r0
drdr0:
(151)
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
aldensity 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
aldensity approximations give "N +1;N +1 =
"N;N +1 . In pra
ti
e, only nonlo
al, orbitaldependent 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 KohnSham
potentials that in
lude the ex
hange part x of x
= x +
. Krieger, Li, and Iafrate (KLI)
[601 show how the KohnSham 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
tex
hange potential, the so
alled optimized ee
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 simplied 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
tex
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 HartreeFo
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: EXXKS are the KohnSham gaps
"N;N +1 "N;N ; EXXx are the SCF gaps "N;N +1 "N;N + x ; and KLIKS are the KohnSham gaps obtained with the approximation suggested by Krieger, Li and Iafrate. The
KohnSham 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 bandgap dis
ontinuity of the
ex
hange potential, are
lose to the HartreeFo
k values and overestimate the experimental
gaps by 5{8 eV. The good agreement between experiment and the EXX KohnSham gaps
together with the large values of x (5{10 eV) implies that
is equally large but negative.
Generalized KohnSham s
hemes. A dierent solution to the bandgap problem has been
proposed by Seidl et al. [610. The KohnSham equations are generalized so that more of
the gap is given by the KohnSham gap and less by the dis
ontinuity. Formally, this redistribution is a
hieved by modifying the original partition of the totalenergy 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 dened through the
onstrained sear
h approa
h. In su
h a formulation, the KohnSham potential is nonlo
al.
One generalized KohnSham theory dis
ussed by Seidl et al. is based on exa
t in
lusion
of ex
hange. In the original KohnSham formulation, for nondegenerate ground states, the
kineti
energy fun
tional is dened by minimizing the kineti
energy operator T^ over all
99
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 (metalsemi
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 mediumgap
materials, as shown in Fig. 50. For largebandgap 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 ee
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 KohnSham 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 KohnSham theory for innite 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 KohnSham ele
trons besides the physi
al eld. In general, for longitudinal,
s
alar potentials we
an dene 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 KohnSham theory for innite insulators the
name `densitypolarization fun
tional theory.'
The problem with the band gap mismat
h between the quasiparti
le and the KohnSham
spe
trum has now been put in a dierent 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 KohnSham pi
ture is very dierent 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 KohnSham ele
trons inherently will not have the
orre
t bandstru
ture and must therefore be driven by a
titious
additional ele
tri
eld whi
h exa
tly
ompensates for the spe
tral dieren
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 densityfun
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 dene the parameter
to be the assumed
onstant of proportionality between
the ex
hange
orrelation ele
tri
eld and the polarization, Ex
=
P. From the denition
of the sus
eptibility , P = EH , where EH is the physi
al (Hartree + external) eld, we
obtain Ex
=
EH . Further, in the KohnSham pi
ture we have P = KS (EH + Ex
). That
is, the KohnSham 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
independentparti
le sus
eptibility given by the KohnSham band stru
ture. By
onstru
tion, the polarization must be the same in both pi
tures. This yields
P
(147)
= 1=KS
1=:
(148)
Due to the too small gap in the KohnSham spe
trum, we expe
t KS > and therefore
that
is negative. Further from the assumption that the main dieren
e between the quasiparti
le spe
trum and the KohnSham spe
trum resides in the energy dieren
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 ee
ts, or the longwavelength limit
an
be taken in the innitesample results. Here we adopt the latter approa
h and fo
us on
the longwavelength limit of opti
al response in the type of bulk formulations we use in the
previous se
tions.
In Appendix A, we dene 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 KohnSham 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 KohnSham 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 KohnSham 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 groundstate density. For the KohnSham ele
trons this indu
ed potential
must be added to the indu
ed Hartree potential. The total indu
ed potential a
ting on the
KohnSham ele
trons therefore is
Vind (r) =
jr
(145)
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 dierent language, the 1=q 2 divergen
e of Kx
means that the KohnSham ele
trons feel a ma
ros
opi
potential dierent 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 longwavelength
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 ee
t of lo
al elds on the diele
tri
onstant, the se
ondorder 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
aleld
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 ee
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 timedependent
urrentdensity
fun
tional theory.
32. DENSITYPOLARIZATION FUNCTIONAL THEORY
In the stati
limit, the indu
ed response to a weak perturbing potential
an be obtained
from a groundstate
al
ulation and should therefore be obtained exa
tly by KohnSham
perturbation theory. This fa
t has always been the strong, and just, argument made by
opponents to the s
issorsoperator approa
h, whi
h arti
ially adds a nonlo
al potential to
a theory that should be able to give the
orre
t lowfrequen
y opti
al reponse by using an
appropriate KohnSham potential. However, there is no doubt that LDA does not su
e due
to the bandgap problem, and there are indi
ations that even in exa
t KohnSham 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 innite sample the ex
hange
orrelation potential in
KohnSham theory
an be divergent in the longwavelength 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 innite 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 innite extent should be taken. This limit
an be approa
hed in
two ways: either the innitevolume limit
an be taken for the nitesize theory in a weak
94
out only re
ently by Chen et al. [573. Earlier work had invariably assumed that only the
linear lo
alelds are important in nonlinear response. However, Chen et al. show that the
nonlinear lo
al elds are of equal importan
e. For example, for se
ondharmoni
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
aleld
orre
tion
ompared to previously published results. The typi
al
orre
tion due to lo
al elds is therefore about 15% for se
ondharmoni
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 ee
t of
lo
aleld
orre
tions. The planewave 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 longwavelength 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
itygauge and
lengthgauge approa
hes and nd that a simpler formulation than the Levine{Allan approa
h
an be obtained when working in the length gauge. The lengthgauge 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
issorsshift approa
h using an LDA FLAPW (fullpotential linearized augmented planewave) band stru
ture, but no lo
aleld
orre
tions are
in
luded. The formulation of Aversa and Sipe is also implemented by Rashkeev et al. [576
using an LMTO (linearized muntin orbitals) bandstru
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
issorsshift approa
h. Adolph and Be
hstedt [578
al
ulated the frequen
y dependent
(2) for GaP, GaAs, InP, InAs and SiC with a planewavepseudopotential method at the
theoreti
al latti
e
onstants. They use s
issors shifts for the IIIV
ompounds but dis
uss a
more sophisti
ated momentum and banddependent selfenergy shift in SiC.
The opti
al response
al
ulations des
ribed so far have been done by sumoverstates
methods, but an alternative exists. Dal Corso et al. [552 use the so
alled `2n + 1' theorem
[579 to derive a dierent and more e
ient numeri
al method for se
ondorder response
within timedependent density fun
tional theory. The 2n+1 theorem in this
ontext expresses se
ondorder response fun
tions (derivable from thirdorder derivatives of the total
energy) in terms of rstorder
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 ae
ts their values. However, their method should lead to the same results as others
at the experimental latti
e
onstants.
The relatively modest lo
aleld
orre
tions we have seen up to this point are not a
general rule. Jonsson et al. [583
al
ulate the lo
aleld
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
issorsshift 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
aleld ee
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 timedependent lo
aldensity approximation [570, rater than in RPA (timedependent Hartree approximation). In this extension, ex
hange and
orrelation ee
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
aleld
orre
tions to the diele
tri
onstant. Invariably a redu
tion of " by 5{10% is obtained. These results are
onsistent
with the the ee
t of lo
aleld
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
ondorder response, the lo
al elds give a larger
orre
tion { generally redu
ing
(2) , but o
asionally in
reasing it. Table 37 shows the ee
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 nonzero se
ondorder 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
aleld
orre
tions are of the order of 1020%, 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
issorsoperator approa
h works well for the
smallergap materials, but an over
orre
tion is obtained for the largergap materials, here
exemplied 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
ondharmoni
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
troopti
oe
ient given by (2) (! ; !; 0) in
ontrast to the se
ondharmoni
oe
ient (2) (2! ; !; ! ). The se
ondharmoni
(SH)
oe
ient
gives the polarization at 2! indu
ed by a eld at ! , while the ele
troopti
(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 { fullpotential linearized augmented planewave) [556, and 104.8 (LMTO
{ linearized muntin orbitals) [576. All these
al
ulations were done with s
issorsshifted
LDA band stru
tures. Clearly, both more experimental and theoreti
al work is
alled for.
The theory for lo
aleld
orre
tions to nonlinear response has been
orre
tly worked
92
h kjvk + qi = h kj
"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
issorsoperator approa
h is used, it is
ru
ial to re
ognize the dierent 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
issorsoperator approa
h, whi
h requires:
h
kjrkHkjvki = h
kjrkHkLDAjvki ;
(143)
"vk "
k +
"vk "
k
91
1 appears on the
Note that only the G0 = 0
omponent of the inverse diele
tri
matrix "GG
righthand side of Eq. (136), sin
e the external opti
al eld has no lo
aleld
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 dened by "(q; ! ) = Vext (q; ! )=Vtot;0 (q; ! ). When
lo
al elds are disregarded, we have "(q; ! ) = "00 (q; ! ), but when lo
aleld ee
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 timedependent Hartree or random phase approximation
(RPA) the diele
tri
matrix is that given in Se
tion 5 in terms of the independentparti
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
fi (1 fi )
fi (1 fi )
;
+
"i "i + ! + i "i "i ! + i
0
(139)
whi
h is an extension to in
lude lo
aleld ee
ts of the Ehrenrei
h and Cohen formula for
the diele
tri
onstant in a solid [110.
In the s
issorsoperator approa
h, the
ondu
tionband energies in the denominator of
0 (q; ! ) are shifted by . Without lo
al elds, the stati
the AdlerWiser formula for PGG
sus
eptibility , dened 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 spinorbit
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 bandgap materials (Egap >4 eV), GWAbased s
issorsoperator
orre
tions frequently lead to an underestimation of " that is as large as the overestimation by LDA. This
ee
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 ee
t on the opti
al response of the quasiparti
le
weight Z that multiplies the singleparti
le Green fun
tion (see Eqs. (7), (8), (18), and Se
tion 11) Within the independentquasiparti
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 higherorder 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
tronhole 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 ee
t of vertex
orre
tions, whi
h are
also negle
ted in the GWAbased s
issorsoperator 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 quasiparti
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 bandgap in
reases. The
on
lusion is that we la
k
a rstprin
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 bandgap 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 kspa
e summations in Eq. (132).
The most important regions in kspa
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
ee
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 KramersKronig 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
issorsoperator approa
h,
sin
e the wave fun
tions are the same by
onstru
tion. The only ee
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 bandstru
ture and manyele
tron ee
ts, the mismat
h
between the LDA and the experimental regions of strong opti
al absorption is not related
to the bandgap 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
ee
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
rstprin
iples argument for what to
hoose is therefore hard
to nd, and the s
issorsshift 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
aleld
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 spinorbit
orre
tion), whi
h is about 0.3 eV larger than a fully relativisti
allele
tron
al
ulation. In
ontrast to GaAs, the bandgap 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 ee
ts in Table 33 for Ge and GaAs from the negle
t
of relativisti
ee
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 (dieren
e between the last two
olumns in Table 33) with the gap
orre
tions from various approximate GWA s
hemes: rstorder perturbation theory; self
onsistently updated band energies; and in
lusion of
orepolarization. The most a
urate
values (last
olumn) show that GWA
orre
tions in
luding
ore polarization ee
ts added
onto fully relativisti
, allele
tron LDA energies do indeed
ome within 0.1 eV of experiment.
However, other levels of approximation yield dierent
on
lusions. For example, pseudopotential
al
ulations that negle
t spinorbit 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 0.10.3 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 selfenergy
orre
tions. However, su
h a
laim is
ountered
by the fa
t that fullyrelativisti
LDA allele
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 momentumdependent selfenergy to the denominator in Eq. (132), but this is in general too
omputationally
ostly. An often used
simpli
ation,
alled the `s
issorsoperator approa
h,' is to add a
onstant, energy and
momentumindependent shift to the
ondu
tionband energies, leaving the valen
e ener87
= 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 nonzero
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 independentparti
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 singleparti
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 selfenergy
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 spbonded 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 higherorder response, the error due to the too small gap
be
omes even worse, sin
e for ea
h order the power of the energy dieren
es in
reases by one
in the denominator of the formulas for the response
oe
ients. Hen
e, the primary fo
us in
opti
alresponse 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
eort, 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 dierent approximations ae
t the LDA gap. The table shows, from left to right,
the importan
e of s
alar relativisti
ee
ts with frozen
ore states, spinorbit intera
tions
(fully relativisti
), and relaxation and hybridization of
ore states. In GaAs, all these ee
ts
are important if we aim at an a
ura
y of 0.1 eV for bandgap 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
[532
Vlo (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
, imagelike behavior, and (ii) inside the metal surfa
e, selfenergy
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 dieren
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 nearsurfa
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 ee
tive oneparti
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, oneparti
le potential of
hoi
e is the so
alled jelliumsphereba
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 WignerSeitz 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 selfintera
tion { the so
alled selfintera
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. Selfintera
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 selfintera
tion errors are small in standard GWA [524.
Remaining quantitative dieren
es with experiment are attributed to the jelliumsphereba
kground model and nite temperature ee
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 selfintera
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 ee
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 ee
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
esensitive experimental te
hniques su
h as lowenergy ele
tron
dira
tion [526, 527, s
anning tunneling mi
ros
opy [528, 529, and inverse and twophoton
photoemission experiments [530, 531 are therefore expe
ted.
The nonlo
al, energydependent, manybody ee
ts that
ause the asymptoti
inverse
power law behavior of the image potential are
ontained in the GWA selfenergy. To obtain a
lo
al, statedependent potential Vlo
(r) from the nonlo
al selfenergy that
an be
ompared
with the lo
al image potential and the LDA ex
hange
orrelation potential Vx
LDA one denes
83
self
onsisten
y. This estimate suggests that all published results for w miss physi
al effe
ts that are as large as the dieren
e between the Jensen{Lyo{Plummer experimental data
[505, 506 and nearlyfreeele
tron theory [514. Consequently, a quantitative analysis and
unied 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 lifetime ee
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 0.250.30 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. Selfenergy 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 selfenergy of, for example, freeele
tronlike s states than
for the selfenergy of strongly
orrelated d states. The dierent
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 holehole 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 rstprin
iples Tmatrix
al
ulation
[71 in
ludes the negle
ted holehole 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 nearlyfreeele
tron theory in two important
ways: (i) the measured band width is about 0.6 eV smaller than the nearlyfreeele
tron
value of 3.2 eV, and (ii) sharp, nondispersive peaks in the energy gap
an be identied for
photon energies of about 35 eV, whi
h peaks have no equivalent in nearlyfreeele
tron theory. Selfenergy
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 dierent
physi
s. Dieren
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 dierent te
hniques.
Selfenergy ee
ts and surfa
eindu
ed momentumnon
onserving ex
itations a
ount
ea
h for about half of the observed Na bandwidth
orre
tion [229, 241, 265. The latter
ee
t also provides a possible explanation for the experimentally observed nondispersive
peaks around 35 eV in the photoemission spe
trum shown in Fig. 43. The in
lusion of surfa
e
ee
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 56
A in Na, i.e., photoele
trons probe
only the rst two to three layers of the material. Mahan et al. use RayleighS
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 RPAbased GWA
al
ulations
by (i) in
luding LDA vertex
orre
tions in the diele
tri
s
reening but not in the selfenergy,
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 fulllment 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 bandwidth 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
aleld fa
tor are in
luded in the
diele
tri
fun
tion, and (ii) dynami
al vertex
orre
tions to se
ondorder in the s
reened
intera
tion W are in
luded in the selfenergy. In
ontrast to Mahan [10, Shirley suggests
that a dynami
al vertex
orre
tion to the selfenergy 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 bandwidth redu
tion w of jellium at rs = 4 suggest that (i) nonself
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
orevalen
e ex
hange for
the energydependen
e of the selfenergy, 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. Corevalen
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 identied 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 selfenergy
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 nonlo
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 110 eV to the
ondu
tion band
ele
tron selfenergy 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
selfenergy 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 semiquantitative 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 ee
tive
rystal potential in alkali metals seems to permit a nearlyfreeele
tronmodel [504 des
ription of the
ondu
tion ele
trons and seems to oer an experimentally a
essible system whose manybody
orre
tions are (i) weak, allowing the use
of perturbation theory su
h as GWA, and (ii) not
ompli
ated by the ee
ts of a
omplex
band stru
ture. However, the experimental determination of the o
upied band width w
80
dimensional transpolya
etylene (trans(CH)x ) [488 { the simplest prototype of a
ondu
ting
polymer { and a quasitwodimensional 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
).
Transpolya
etylene. In trans(CH)x [488, GWA leads to a 68% redu
tion of the initial HartreeFo
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 HartreeFo
k gap only to 3.1 eV [488. The
theoreti
al ele
tronenergyloss spe
trum shows a lowenergy 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 Silayer polysilane
ompound [489 exhibits strong quantum
onnement ee
ts with strong quasidire
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. Selfenergy
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 \zerodimensional" systems. GWA
al
ulations for mole
ules have only
been reported for quasionedimensional and quasitwodimensional 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 highT
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
orevalen
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 HartreeFo
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 HartreeFo
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 HartreeFo
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 HartreeFo
k and the LSDA, (ii) GWA reprodu
es experimental trends qualitatively for the se
ond half of the iron series in
ontrast to HartreeFo
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
reenedex
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 twobody
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 \zerodimensional" atoms, quasiparti
le
al
ulations have been done for quasione78
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 zeropoint 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 dieren
es in ele
troni
energies between dierent
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 exemplied by a metalinsulator 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
{ dened 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 metalinsulator transition pressure of more than 300 GPa seems likely [473.
24. EXCITONS
Intera
ting ele
tronhole 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 lowlying ex
ited states are de
reased,
and (ii) the
orresponding os
illator strength is in
reased. Semiempiri
al tightbinding
results of Hanke, Sham, and
ollaborators (see Se
tion 9 b) for Si show about an eV shift of
the energies of lowlying 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 HankeSham approa
h by using rstprin
iples rather than semiempiri
al wave fun
tions and band energies.
Appli
ations to bulk semi
ondu
tors and widegap insulators (Si, Ge, GaAs, diamond, Li2O,
MgO, LiF; Refs. [56, 474, 475, 476, 477)
onrm Hanke's and Sham's
on
lusions regarding
the shift of lowlying 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
ee
ts are more important in largegap insulators
than in small and mediumgap semi
ondu
tors, sin
e s
reening is less ee
tive in the former.
Corehole ex
itons have been studied in LiF, NaF, KF, graphite, diamond, and hBN [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
onned 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
tronhole intera
tion results
77
[456, 457, solid mole
ular hydrogen [457, 458, and diamond [459. Other possible s
enarios
for metalinsulator transitions in
lude stru
tural transformations as is the
ase for Si under
pressure [460 and simultaneous magneti
and metalinsulator transitions as in NiI2 [461. To
date, quasiparti
le
al
ulations for stru
tural or magneti
metalinsulator transitions have
not been attempted.
The simplest estimate of the metalinsulator 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 twoband 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 selfenergy 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 metalinsulator 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 spinorbit
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 highpressure behavior of diamond is of parti
ular interest due to the
wide spread use of diamondanvil
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 diamondanvil
ells is not fully known,
whi
h may explain the underestimation of the experimental diamond metallization pressure
of 700900 GPa [468 by GWA
al
ulations [459 that predi
t a metallization pressure of 400
GPa for an idealized geometry.
The selfenergy
orre
tion to the LDA band stru
ture of solid mole
ular hydrogen shows
a nonlinear 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, HartreeFo
k,
and GWA. For low densities (atmospheri
pressure) the selfenergy
orre
tion to LDA is
large sin
e this regime is dominated by ex
hange and GWA is
lose to HartreeFo
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 dierent in LDA and quasiparti
le
al
ula76
22. DEFECTS
Defe
ts in semi
ondu
tors ae
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 30100% 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 statedependent
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
onne 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
onned to nearestneighbor alkalimetal 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 intradefe
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 intradefe
t ex
itation, ex
itoni
ee
ts
must be in
luded in the determination of the quasiparti
le transition energy. These ee
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 3.13.3 eV [455.
Besides ex
itoni
ee
ts, quasiparti
le defe
t
al
ulations are
hallenging due to problems
related to nite size ee
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 metalinsulator 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
estate 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 selfenergy
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 selfintera
tion errors are largely eliminated in GWA leading to the large selfenergy
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
sulphurterminated 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 dierent 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
ombinationofatomi
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
onsistent improvement over LDA of
al
ulated valen
e band osets
ompared to experiment
an be a
hieved [413.
Further appli
ations. An overview over valen
e band oset
al
ulations in the GWA
and expli
it
al
ulations for the Inx X1 x AsIny 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 bondlength
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 1001000
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 ntype (ptype) 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 ntype and
ptype S
hottky barriers Bn and Bp are dened 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 2060% of the LDA barrier depending on the parti
ular
interfa
e stru
ture
hosen and establishes the importan
e of manybody
orre
tions.
Selfenergy ee
ts lead not only to
orre
tions to the S
hottky barrier height but also
to semi
ondu
tor bandgap narrowing in the 110
A vi
inity of the metalsemi
ondu
tor
interfa
e [425, 426. Classi
ally, an ele
tron in the semi
ondu
tor experien
es an additional
energylowering, ele
trostati
potential whose ee
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 (
orepolarization ee
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
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 dieren
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 GaAsAlAs 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 metalva
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 oset at a GaAsAlAs interfa
e [410, 417
amount to about 0.1 eV or 30% of the valen
e band oset of 0.41 eV determined in LDA.
Selfenergy
orre
tions are
ru
ial to obtain a theoreti
al valen
e band oset of 0.530.05
eV in good agreement with experimental values of 0.530.56 eV [418, 419.
As in the
ase of GaAsAlAs, Table 28 shows that quasiparti
le ee
ts in
rease the
valen
e band oset at a zin
blende GaNAlN (110) nonpolar interfa
e by about 30% or
0.25 eV [196. The size of the selfenergy
orre
tion for the nonpolar interfa
e as well as the
large dis
repan
y between experimental valen
e band osets for the polar wurtzite GaNAlN
(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 selfenergy
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 oset 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 IIVI 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.
Dieren
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 osets pushes the a
ura
y limits of the GWA. Nevertheless, a
71
in photo
urrent experiments [407. Dire
t, zonefolded transitions are predi
ted at 1.24,
1.34, 1.76, and 1.86 eV and explain features observed in ele
trore
e
tan
e measurements
at 1.11.25 and 1.8 eV [407. For a Ge substrate, Si4 Ge4 is predi
ted to be approximately a
dire
tgap semi
ondu
tor.
Connement of states in either the Si or the Ge region of the superlatti
e should not have
a signi
ant quantitative ee
t on the expe
tation value of the selfenergy operator sin
e the
selfenergy ee
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. Bandgap variation and variation of dire
tindire
t bandgap 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
AlAsregion of the superlatti
e, due to the relative repulsive
hara
ter of the Al versus the
Ga pseudopotential. This lo
al bonding ee
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 ee
tivemass
model
al
ulations. Ee
tive mass
al
ulations (i) miss the lo
al bonding ee
t, and
onsequently (ii) show an inverted ordering of bands [411.
b. Interfa
es
An interfa
e between two dissimilar semiinnite semi
ondu
tors A and B is
hara
terized
by the dieren
e in the valen
e band energy between the two bulk regions, the valen
e band
oset Ev , and the
orresponding
ondu
tion band oset E
[413 as shown in Fig. 34.
Interfa
es play an essential role in heterojun
tion devi
es, and the band osets Ev and E
determine their transport properties [414. The qualitative ee
ts of interfa
e orientation,
defe
ts, polarity, and strain on band osets
an be studied using density fun
tional theory.
However, a more a
urate predi
tion of valen
e and
ondu
tion band osets requires a quasiparti
le approa
h [413. Sin
e the sum of the valen
e and
ondu
tion band osets equals the
known band gap dis
ontinuity between the semi
ondu
tors A and B, Egap = Ev + E
,
selfenergy
orre
tions of only the valen
eband oset 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 bulkderived valen
e band edge
positions to obtain a band oset for a parti
ular interfa
e. Let the volumeaveraged [415,
ele
trostati
(Hartree) potential hVH iA(B) dene 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 dieren
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
3.53.7 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 1.61.7 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 bandwidth narrowing within a quasiparti
le framework.
Four
auses for a la
k of dispersion in angleresolved 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 SlaterKoster 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
tronele
tron
orrelations
[338, 394.
Further appli
ations. Bandwidth 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
onnement, builtin strain, Brillouin zone folding, and twodimensional ele
tron gas
behavior [403, 404, 405. Variation of superlatti
e
hara
teristi
s permits fabri
ation of
semi
ondu
tor devi
es with
ustomtailored 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
tgap semi
ondu
tors Si and Ge, sin
e this stru
ture
(i)
ould be a pseudodire
tgap material suitable for optoele
troni
appli
ations, and (ii)
is
ompatible with Sibased
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
modelGWA 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
onrmed 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 oneparti
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 modelGWA
al
ulation of Massidda et al. is the separation
of the s
reened intera
tion W into a shortrange part W IEG that des
ribes the s
reening of
an inhomogeneous ele
tron gas and a longrange part W that a
ounts for the in
omplete
s
reening in insulators [381. The shortranged
ontribution W IEG is approximated by the
lo
al, energyindependent KohnSham ex
hange
orrelation potential [39. The longranged
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 transitionmetal 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 selfintera
tion
orre
ted
al
ulations. The inability of RPAbased GWA to reprodu
e the satellites in photoemission
spe
tra is attributed to the la
k of shortrange
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 onmole
ule and nearestneighbormole
ule HubbardU 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. Selfenergy
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 2.32.7 eV dedu
ed from dire
t and indire
t photoemission experiments [397,
398, 399. The Hu T1u peaktopeak 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 rstorder perturbation theory and negle
ting the unimportant Hartree
ontribution the
quasiparti
le bandgap
hange equals
Enk =
EV BM
(125)
(124)
whi
h even for as high ele
tron
on
entrations as n = 4 1020
m 3 ae
ts the band gap by
less than 5 meV [375.
In a GWA
al
ulation
ontributions to bandgap narrowing result from (i) a
hange in
the s
reening of the ele
tronele
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
orepolarization
and
orerelaxation ee
ts [43 and s
alarrelativisti
, allele
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 planewaves [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 dieren
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 dieren
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
lelike 15v and L1
states [114.
GaN is a very important material for opti
al devi
es su
h as blue lightemitting 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 sd 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 planewave
al
ulations of Refs. [42, 47, 367. Variations in the
quasiparti
le energies of the lowestlying
ondu
tion band for the three dierent
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 dierent
pseudopotentials as spe
ied 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 CeperleyAlder 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 osets [357. Note that the selfenergy
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 dened, 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
ee
ts. The
ore
an in
uen
e the valen
e energies in several ways: (i)
ore
relaxation, (ii)
orevalen
e ex
hange, (iii)
orevalen
e
orrelation, (iv )
ore polarization.
As shown in Se
tion 12, an improved treatment of ex
hange and
orrelation ee
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
alarrelativisti
GWA
al
ulations for Ge that
treat
orevalen
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 0.10.3 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 ae
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
orevalen
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 dierent
al
ulations due to dierent 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 Rohlng 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) Plasmonpole approximations do not ae
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 materialdependent. 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
planewave
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
ee
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 plasmonpole 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 plasmonpole 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 selfenergy. 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) ae
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 lowlying 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 selfenergy 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, planewavebased GWA
al
ulations whose
LDA ex
hange
orrelation is based on the CeperlyAlder data for the homogeneous ele
tron
gas [355. For these
al
ulations, the main selfenergy
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
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 rve
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 rve
tors in FFT order.
Although the Green fun
tion is
onstru
ted with
lose to perfe
t load balan
ing by parallelizing over the rve
tors in the irredu
ible realspa
e unit
ell, the load balan
ing for the
onstru
tion of the independentparti
le polarizability in re
ipro
al spa
e is less favorable
sin
e now the symmetry of the rve
tors in the irredu
ible realspa
e unit
ell is important
as well. However, larger systems have many rve
tors in the irredu
ible realspa
e unit
ell
and low symmetry and dieren
es in symmetries should average out.
After all these steps, one obtains P 0(k; G; G0 ; i ) for all Gve
tors and a blo
k of G0 ve
tors whi
h is written to disk via PE0 for all kpoints 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 independentparti
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 onetoall
broad
ast and singlenode 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, kpoints,
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 rve
tor
in the real spa
e unit
ell. The re
ord
ontains unk(r) for all bands and all kpoints. For
unk (r0 ) the re
ord index is the number of the spe
ial kpoint 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 nonintera
ting propagator
at imaginary times i and for all rve
tors in the irredu
ible realspa
e unit
ell is determined. Ea
h PE has a list of rve
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 rpoints in the irredu
ible realspa
e unit
ell is 55 and the number of pro
essors
is 4, then PE0
al
ulates G0 for the rst 13 rve
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 kpoints as well
as unk(r0 ) for all r0 , all bands, and all kpoints. 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 kpoints, PE0 reads unk (r0 ) for a parti
ular kpoint
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 kpoints and has
al
ulated
its nonintera
ting propagator at i it sends the produ
t G0 (ri ; r0 ; +i )G0 (ri ; r0; i ) { i.e.
the independentparti
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 independentparti
le polarizability for dierent ve
tors ri
in the irredu
ible realspa
e unit
ell and distributes P 0(ri ; r0 ; i ) over the dierent pro
essors
in an analogous way as is done for the distribution of unk(ri ). Within an external loop over
spe
ial kpoints 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 rve
tors in the irredu
ible realspa
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 rve
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 kpoint and send the results of their
al
ulation
ba
k to PE0. PE0 then assembles the total polarizability. Therefore, for a xed kpoint,
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
oarsegrain parallel
ode ensures
portability to dierent platforms [332. The use of symmetry as des
ribed in Eq. (116) does
not require any interpro
essor
ommuni
ation sin
e the matrix elements for all Gve
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 kpoint, at whi
h the wave fun
tion is dened,
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 embarrassinglyparallel approa
h of distributing kve
tors over PEs [333, (ii) a parallelization over re
ipro
al Gve
tors [334, and (iii) a
parallelization over
ondu
tion bands. Changing the
ode to a
ommodate new parallelization s
hemes proted immensely from the
exibility that an obje
toriented programming
style oers
ompared to a pro
edureoriented programming style.
0
58
lines of
ode). The
lass wavefun
tion
ontains the kpoint at whi
h the wave fun
tion is
dened, 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 independentparti
le polarizability
[
f. Eq. (101) from the wave fun
tions. They
an be used as well for the plasmonpole
eigenve
tors (also of type wavefun
tion) and the
onstru
tion of the selfenergy 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 lowlevel 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 CRAYYMP8 (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 dieren
es in pseudopotentials,
parametrization of ex
hange
orrelation potentials, and the like, whi
h plague input to selfenergy
al
ulations using dierent 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
edureoriented
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, modied, or extended beyond
the realm of its initial use [328.
An obje
toriented 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 userdened 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
torve
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 dierent
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
alspa
e GWA
ode of Ref. [42 is written in C++ in an obje
toriented style.
Data abstra
tion at a lowlevel is a
hieved through extensive use of an inhouse C++library
that denes 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
utos used for Si as well as
utos 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 dier from material to material and have to be repeated for every
material under
onsideration. Convergen
e studies as a fun
tion of the energy
uto and the
number of kpoints are
ostly, sin
e a new plasmonpole band stru
ture has to be generated
ea
h time. Often
onvergen
e studies
an be limited to two and ten spe
ial kpoints. An
appropriate energy
uto
an be determined by
hoosing it large enough to
onverge LDA
valen
e and lowlying
ondu
tion band energies to within 50 meV. For example, for Si an
in
rease in energy
uto 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 plasmonpole models
Dieren
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, Rohlng et al. [52, 114 and Ba
kes et al. [130 use Ba
helet{Hamann{
S
hluter pseudopotentials [324, and Ref. [42 uses soft TroullierMartins pseudopotentials
[325. Deviations for well
onverged LDA and GWA
al
ulations from dierent 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 TroullierMartins 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 lowlying
ondu
tion
bands. Corresponding deviations for selfenergy 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 plasmonpole models and shows that the
hoi
e of dierent 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 dieren
es in the band stru
ture of nearlyfreeele
tron metals using the Hybertsen{Louie model
ompared to an earlier
al
ulation by
Lundqvist [98 that uses a dierent plasmonpole model.
e. Obje
t orientation
The
ommon
omputing paradigm in most s
ienti
appli
ations is pro
edureoriented programming. The
entral task of a software engineer using the pro
edureoriented paradigm is
55
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 lowlying
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
dieren
es in (i) the number of qpoints used in the integration of Eqs. (104) and (105),
(ii) the energy
uto used in the expansion of the LDA wave fun
tions, (iii) the number
of singleparti
le and plasmonpole bands kept in the summations in Eq. (105), (iv ) the
number of Gve
tors kept in the summation in Eq. (106), and (v ) the degree of
onvergen
e
of the plasmonpole band stru
ture. To determine reliable quasiparti
le band stru
tures all
these numeri
al
utos have to be
he
ked systemati
ally. Convergen
e with respe
t to the
numeri
al
utos mentioned in (i) (iv ) is generally smooth [320 as
an be inferred from
Figs. 2427 and Table 17. Details of the
al
ulations are given in the
aptions. A plot of
54
53
P 0 (k; r; r0) =
IC
(r)
X
R
exp( ik (r
r0
(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 3dimensional FFTs [313. The Fourier transform of the
independentparti
le polarizability is given as (V
is the unit
ell volume) [314
0 (k) = 1
PGG
0
Z Z
V V
(114)
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 dene 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)
(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 kpoints in the full Brillouin zone (BZ)
as a sum over kpoints in the irredu
ible Brillouin zone (IBZ) and over symmetry operations
S that generate the kpoints in the full BZ. One obtains the following formula for G0 whi
h
is implemented in the realspa
e/imaginarytime program
G0 (r; r + x; i ) = isgn( )
o
(X
uno
) IBZ
X X
n
(111)
Assuming an intera
tion
ell that is of
onstant size for a given material, the determination
of the independentparti
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 rpoints 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 realspa
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 rpoints 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
(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 shortranged 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 shortranged (
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 longrange tail
an be taken into a
ount expli
itly [103 allowing the use of a
nite
uto 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 imaginaryfrequen
y (and
imaginarytime) 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.
ati
ally
onverge,
onstru
ting su
h basis sets is di
ult. Table 15 demonstrates the problems in establishing the energies of lowlying
ondu
tion states of smallgap and mediumgap
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 lowlying
ondu
tion and valen
e states
to within 0.1 eV [114. While this is true for Si [114 and for largegap materials with
strongly lo
alized densities su
h as diamond, SiC, and GaN [295, good
onvergen
e for
more \metalli
," small and mediumgap 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 planewave and a 40Gaussianorbital
al
ulation dier by up to 0.3 eV in LDA and up to 0.6 eV in GWA, (ii)
higherlying states su
h as the L02
state dier by up to 1.3 eV in LDA and 1.6 eV in GWA,
and (iii) the Gaussianorbital results
onverge systemati
ally towards the planewave 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 lowlying
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) ae
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 nonlinear
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
alarrelativisti
TroullierMartin pseudopotentials in the KleinmanBylander form [304.
Semirelativisti
, nonlo
al abinitio pseudopotentials [51 give an energy gap of 1.36 eV when
nonlinear
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
alarrelativisti
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 dierent
Cd2+ pseudopotentials amount to at least 0.5 eV and are on the order of the selfenergy
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
IIVI materials via nonlinear
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
uto and several thousand plane waves. In LMTO, the des
ription of
transitionmetal oxides uses only 50100 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 muntin 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 selfenergy operator. (ii) The
atomi
sphere approximation assumes a spheri
ally symmetri
potential. This shape approximation
an ae
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 fullpotential 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 allele
tron LMTO results for GaAs [290 with
pseudopotential results that in
lude
orepolarization potentials and
ore relaxation ee
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 lowlying
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 fullpotential 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, Rohlng, 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 Gaussianorbital basis set.
The merit of Gaussianorbitalbased 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 exemplied 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
ee
ts in Sin Hm
lusters
[282.
The main disadvantage of Gaussian orbitals is that while Gaussian basis sets
an system48
pnm (k; q) =
(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
alspa
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
plasmonpole eigenve
tors. The selfenergy itself (Eq. (105)) must be determined via a sum
over LDA bands and a sum over plasmonpole 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 selfenergy [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 densitydensity response fun
tion with an O(NP3 W ) eort, but have not been
extended to the
al
ulation of the selfenergy.
(100)
Dene 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 (G0
G) k (G0 ):
(101)
2
V
o uno BZ
X X X
"v k
" k
! + i
"vk
" k + ! + i
(102)
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 plasmonpole 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 lowlying valen
e states as is
demonstrated in Table 21. Splitting the selfenergy into a bare ex
hange part X and an
energydependent
orrelation
ontribution C (E ), as detailed in Se
tion 6, gives
46
. Plane waves
General remarks. Pseudopotentials in
onjun
tion with a planewave basis set are widely
used in
omputational
ondensed matter theory due to their ease of use and systemati
onvergen
e properties [275. Mostly, planewavebased GWA
al
ulations are applied to
spbonded 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 planewave basis sets are (i) the number of plane waves
NP W in
reases with the system volume V and the energy
uto 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
alorbital basis sets dis
ussed below.
Re
ipro
alspa
e GWA
al
ulations s
ale as NP4 W (see below) whi
h
auses planewavebased
GWA
al
ulations for largeV 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
ee
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
selfenergy 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 plasmonpole model [271. The results of adding the lowestorder vertex (V)
and selfenergy (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 longwavelength limit [119, 272 and provides a formal motivation for
an in
lusion of both ee
ts in the polarizability. The ee
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
aleld ee
ts due to an inhomogeneous density distribution.
In
lusion of vertex and self
onsisten
y
orre
tions in the selfenergy 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 dierent
ombinations of
vertex and self
onsisten
y
orre
tions for the polarizability and the selfenergy are shown
in Table 14. The in
uen
e of V+SC
orre
tions to the selfenergy 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 lowestorder vertex and self
onsisten
y
ontributions is far from being
omplete if one determines these
orre
tions to the GWA selfenergy using a nonintera
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 selfenergy
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 ee
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 Wardidentitylike 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
bandwidth narrowing is obtained from a treatment of the inhomogeneous surfa
e potential
and the nite imaginary part of the selfenergy only. Shirley [232
ombines results from
partially self
onsistent GW0 A
al
ulations with stati
vertex
orre
tions in P and dynami
se
ondorder
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 dierent physi
s
ontained in the respe
tive approximations all three approa
hes agree
with the experimental band widths (for example, 0.7 eV bandwidth narrowing in sodium
ompared to the freeele
tron result, see Se
tion 26 b for more details). We estimate that
missing self
onsisten
y ee
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
ondorder 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 nonself
onsistent
GWKx
al
ulation whi
h takes vertex
orre
tions for " into a
ount via the following manybody lo
aleld fa
tor f (q )
k2
f (q ) = Kx
(n) 2 F 2 ;
(99)
kF + 0:08q
where Kx
(n) is dened 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 lowestorder vertex and self
onsisten
y ee
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
ondorder in the intera
tion. The se
ondorder
ontribution
in the bare Coulomb intera
tion to the selfenergy and the energy gap of Si is negligible
ompared to the rstorder
ontribution [88. In a bondorbital approximation [19, 260 the
se
ondorder terms
an be written as the sum of two partially
an
eling
ontributions [260:
(i) the partial blo
king of groundstate
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
higherorder ee
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 bandgap 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 higherorder
orre
tions are in
luded in the selfenergy they are negle
ted in the polarizability in
on
i
t
with Mahan's suggestion [10. The se
ondorder
ontribution partially
an
els the additional
band gap in
rease of 0.7 eV due to self
onsisten
y [230. Ee
ts due to the
onsistent use
of vertex
orre
tions not only in the selfenergy 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 meaneld vertex
orre
tions in the polarizability (GWKx
) or in the
polarizability and the selfenergy (GW ) shows that (i) relative energies are modied by
in
luding vertex
orre
tions only in the polarizability, and (ii)
an
ellation between vertex
orre
tions to the polarizability and to the selfenergy o
ur for relative but not for absolute
energy shifts. The GW approximation uses an LDA ex
hange
orrelation potential [263
as zerothorder selfenergy approximation and
an be expressed in a GWAlike form using
~ and a diele
tri
matrix "~ [89
an ee
tive ele
tronele
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 selfenergy
ause a band gap in
rease that
an
els the ee
t of the
vertex
orre
tions in the s
reening. Note the qualitative dieren
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
ondorder 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
eband oset
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 ee
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 highenergy ex
itations. This is unfortunate,
sin
e the physi
s of high and low energy ex
itations
an dier signi
antly. An example is
the energy dependen
e of the selfenergy 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 selfenergy 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 BetheSalpeter
equation for the vertex fun
tion and has been applied to a twodimensional, 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 selfenergy 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 ee
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 BetheSalpeter 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 selfenergy 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
ondorder in the RPA s
reened intera
tion but also terms
of zeroth and rstorder. 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
(93)
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 dier 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) =
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 independentele
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 ee
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, twoleg Hubbard
ladder is always raised by self
onsistent
al
ulations relative to standard GWA
al
ulations.
This is not only true for RPAbased GWA
al
ulations but also for GWA
al
ulations that
in
lude vertex
orre
tions and for a BetheGoldstone approa
h based on the Tmatrix [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 nonself
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 Hubbardladder spe
tral fun
tion at self
onsisten
y (broadening
of highenergy plasmons, sharpening of quasiparti
le features) agree with the ndings of
Holm and von Barth [231 and of Eguiluz and S
hone [235.
The ee
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
eband
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 nonself
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 GalitskiiMigdal 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 realspa
e/imaginarytime algorithm. In the latter work,
the Hartree potential of Eq. (3) is iterated to self
onsisten
y in the presen
e of a nonself
onsistent GWA selfenergy. 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 nonintera
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) plasmonpole 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 fulll the fsum rule and is only a mathemati
al tool to
determine the selfenergy, 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 justied 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 onedimensional 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 independentparti
le wave fun
tions and energies. We
all
this approa
h the GW0 A approa
h in
ontrast to the nonself
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 dieren
e may
result from te
hni
al dieren
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
leplasmon
ollisions.
38
(ii) the s
reened intera
tion is determined in RPA using the
hosen singleparti
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 plasmonpole 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 selfenergy using Hartree wave fun
tions and energies and iterates the
al
ulation
until self
onsisten
y in G and W is a
hieved. Nonself
onsistent results for quasiparti
le
energies obtained starting from Hartree theory dier from, for example, LDAbased \best
G, best W " approa
hes sin
e Hartree wave fun
tions and energies are qualitatively dierent
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 independentparti
le Green fun
tion su
h
that the Fermi levels of the intera
ting and the nonintera
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 modied 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
(92)
Here Ai and Bi , i = v;
, are tting parameters whi
h are determined via the band gaps at
two highsymmetry points. Note, however, that Ri
e [228 advises against using a shifted
selfenergy sin
e the energy dependen
e of the selfenergy is largely
an
eled by other self
onsisten
y ee
ts. In
ontrast to the energies, the independentparti
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 nonself
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 lifetime ee
ts, i.e., the nite imaginary part of the selfenergy. In most GWA
al
ulations point (i) is treated approximately via plasmonpole 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 justied 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 nonself
onsistent selfenergy 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 ae
ted signi
antly by the s and p
ore ele
trons. Remaining
selfintera
tion errors in the wave fun
tion may
ause errors in the nonself
onsistent GWA
al
ulations on the order of about an eV.
As shown earlier, nonlo
al ex
hange and in
lusion of s
reening ee
ts due to shallow
ore
states are important and ae
t quasiparti
le properties [43, 197, 198. Ex
hange
an have
qualitative ee
ts on the energy dependen
e of the selfenergy 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 515%. The remaining dis
repan
ies with experiment
are partially due to the la
k of self
onsisten
y, vertex
orre
tions, and selfintera
tion errors
in the LDA wave fun
tions.
13. SELFCONSISTENCY
General remarks. Most
urrent GWA
al
ulations have three
hara
teristi
s: (i) the Green
fun
tion is
al
ulated in an appropriate singleparti
le basis following the \best G, best W "
philosophy (HartreeFo
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 twoele
tron potential V^e e is an ee
tive intera
tion between two valen
e ele
trons
due to
orepolarization ee
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 ee
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 densityresponse fun
tions of isolated
ores [43. The
ee
tive intera
tion WC repla
es the bare Coulomb intera
tion in the determination of the
valen
evalen
e selfenergy in the GWA and in the plasmonpole sum rules [43.
Shirley et al. [43 use this modied GWA approa
h and evaluate the selfenergy
orre
tions using LDA wave fun
tions and energies. Self
onsisten
y in the quasiparti
le energies is
a
hieved and
ore relaxation ee
ts are added a posteriori by
omparison of LDA allele
tron
and pseudopotential
al
ulations.
Corepolarizationpotential
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
orevalen
e intera
tions on an LDA level [210.
b. Expli
it treatment of
ore ele
trons
Lo
alorbital 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 ee
ts on the LDA level,
and (ii) ex
hange and dynami
s
reening ee
ts of
ore and semi
ore ele
trons on the GWA
level. The advantage of lo
alorbital basis fun
tions
ompared to planewave methods is the
drasti
ally redu
ed number of basis fun
tions.
In
luding semi
ore d states as valen
e ele
trons in nonself
onsistent GWA
al
ulations
for IIVI 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 selfenergy operator is nondiagonal in the basis of LDA states. Unphysi
al selfintera
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
pd mixing, the LDA states are not good approximations to quasiparti
le states and the
selfenergy is nondiagonal. An iterative determination of quasiparti
le wave fun
tions and
energies in prin
iple eliminates the selfintera
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
eele
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 selfintera
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 ionion 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 ee
ts [201, 202, 203. The rst two ee
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
singleele
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
uto 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 IIVI [188, 189, 190, 191 and of
some IIIV (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 ae
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 1050%
upon in
lusion of semi
ore states [197, 198, 199, and (iii) for higherorder opti
al response
fun
tions su
h as the
oe
ient of se
ondharmoni
generation in
lusion of semi
ore states
an give a su
iently large ee
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 IIVI semi
ondu
tors, some IIIV 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,
energyindependent fun
tional of the total density of the system. However, ex
hange and
orrelation ee
ts between
ore and valen
e ele
trons are nonlo
al and energydependent.
Dynami
orrelation ee
ts o
ur when
u
tuating
ore dipoles intera
t with
u
tuating valen
e densities. These
orrelations modify the ee
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
orepolarizationpotential
(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 ee
ts) and to hybridization of
ore and valen
e orbitals. These ee
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 IIVI materials energeti
ally overlap the valen
e band and hen
e
annot
be eliminated via a
orepolarization 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 planewavebased
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 IIVI materials [51. However, this
agreement must be
onsidered
oin
idental, sin
e it relies upon error
an
ellation between
ore relaxation and
orevalen
e ex
hange and polarization ee
ts.
a. Corepolarization potentials
Dynami
al intershell
orrelation between semi
ore and valen
e ele
trons leads to indu
ed
33
Besides bandgap 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 midgap 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 selfenergy. Hen
e, the
ee
t of the energy dependen
e of the selfenergy, besides the redu
tion in the band gap, is
a signi
ant
hange { from linear to
at { in the dispersion of the bands.
Selfenergy
orre
tions in small and mediumgap 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
issorsshift approa
h works well in Si, it breaks down in widebandgap
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
issorsshift 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 simplied model of the selfenergy of an insulator approximates its nonlo
ality and
energy dependen
e by the
orresponding quantities of the jellium selfenergy evaluated at
the lo
al density in the insulator [185. Figure 12, panel e) shows that the variation of the
selfenergy 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 selfenergy 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 selfenergy:
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 nonlo
ality and energy dependen
e
of the selfenergy of jellium. The fa
tor (f (r)+ f (r0))=2 a
ounts for lo
aleld ee
ts. To the
best of our knowledge appli
ations of this formula have been limited to model
al
ulations.
12. COREPOLARIZATION 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 IIVI materials) in
al
ulations leads to better
32
hole of the selfenergy mirrors the nonlo
ality of the shortranged s
reened intera
tion W
rather than the longranged singleparti
le propagator G. The average radius of the rst
nodal surfa
e of the nonlo
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
tionband wave fun
tion and the
hole a
ounts for more than 99% of the selfenergy expe
tation value in Si. The nonlo
ality
of the selfenergy
ontributes signi
antly to the steplike stru
ture in the selfenergy
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 steplike stru
ture is absent in jellium whi
h indi
ates that although
the overall form (not the depth) of the nonlo
ality hole is well reprodu
ed by jellium at the
appropriate density, the intera
tion between the wave fun
tions and the nonlo
ality is not
aptured in the homogeneous ele
tron gas [185.
Evaluation of the selfenergy operator of jellium at the lo
al density of Si leads to an
underestimation of the selfenergy nonlo
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 SELFENERGY
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 ee
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 selfenergy
in the COHSEX approximation.
The bandgap redu
tion results from the linear behavior of the selfenergy as a fun
tion
of energy
lose to the quasiparti
le energy. Figure 13 shows that the expe
tation values of
the selfenergy 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 dened ex
itations for energies
lose to the band gap although dynami
al ee
ts are
nonnegligible. 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 selfenergy of jellium
[4. Core ele
trons
an qualitatively
hange the energy dependen
e of the selfenergy, as
dis
ussed for the
ase of Ag in Se
tion 26 a.
31
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
aleld ee
ts, and (ii) a strong
lo
aleld ee
t on the expe
tation value of COH for o
upied but not for uno
upied states.
Both expe
tations are
onrmed by a
tual
al
ulations as shown in Tables 6 and 7.
Lo
aleld ee
ts are somewhat weaker for the s
reenedex
hange
ontribution to the
selfenergy 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
aleld ee
ts. Table 7 shows,
that for o
upied states lo
aleld ee
ts in SEX amount to about a third of the lo
aleld
ee
ts in COH and that lo
aleld ee
ts for uno
upied bands in SEX are even smaller.
Sin
e lo
aleld ee
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 ee
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
aleld ee
ts on the selfenergy 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
ovalentlybonded semi
ondu
tors.
b. Nonlo
ality of the selfenergy
The s
reenedex
hange
ontribution to the selfenergy is proportional to the nonlo
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
aleld ee
ts [186. The Coulombhole selfenergy (Eq. (82)) does
not experien
e any nonlo
al ee
ts upon
rossing the band gap sin
e it is a lo
al operator.
Figure 11 shows that the nonlo
ality of the selfenergy (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 selfenergy [185. The nonlo
ality
30
whose diagonal matrix elements a
ount for homogeneous s
reening (see Se
tion 31 for a
detailed dis
ussion). Lo
aleld ee
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 { nonlo
al operators su
h as the selfenergy depend on
two independent realspa
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 selfenergy
orre
tions at the band gap (see below).
The
ombined ee
t of lo
al elds and the nonlo
ality of the selfenergy operator on
the band gap of solids is signi
ant and
annot
learly be separated into two distin
t
ontributions. For instan
e, lo
aleld ee
ts modify the range of the selfenergy. Despite the
interdependen
e of lo
aleld ee
ts and the selfenergy nonlo
ality, the next two paragraphs
dis
uss the dominant in
uen
e of lo
al elds and of nonlo
ality on selfenergy
orre
tions
separately.
a. Lo
al elds
A realspa
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
aleld
ontribution is mu
h smaller (roughly one tenth)
in the lowdensity, interstitial regions, (iii) lo
al elds are responsible for the anisotropy of
the s
reening potential, and (iv ) lo
al elds are shortranged and their ee
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 energydependen
e of
from lo
aleld ee
ts.
The s
reening potential due to an ele
tron at site r evaluated at the same site determines
the Coulombhole
ontribution to the selfenergy 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
aleld ee
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
Coulombhole and s
reenedex
hange
ontributions to the selfenergy
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
itedstate properties have been
reported for Si, Egap = 3:0 eV (3.33.4 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 selfenergy is a shortranged operator [39 and { as a groundstate property { a fun
tional of the ground state density [39. For systems with slowly varying density, a possible
approximation of is given by the selfenergy 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 LevineLouie
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 manybody selfenergy is not
aptured in QPLDA sin
e (i) the
energydependen
e of the QPLDA selfenergy in
reases the LDA band gaps and a
hieves satisfa
tory agreement with experiment, and (ii) lo
aleld ee
ts are not taken into a
ount.
In more a
urate GWA
al
ulations stati
, inhomogeneous s
reening ee
ts open the LDA
band gap of semi
ondu
tors, and dynami
ee
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. LOCALFIELD EFFECTS AND THE NONLOCALITY OF THE SELFENERGY
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 odiagonal 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 denition 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 innite 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
ee
ts via the solution of the BetheSalpeter 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 50100% 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 denition 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 BetheSalpeter equation with respe
t to semiempiri
al tightbinding valen
e and
ondu
tion bands, whi
h are expressed in
a Gaussianorbital 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 ee
ts based on quantum
hemistry methods
starts from a HartreeFo
k wave fun
tion and in
ludes lo
al
orrelations in the form of
one and twoparti
le [173 ex
itations in the manybody 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
itedstate
orrelations and that
an be determined variationally.
Bond polarizations are interatomi
orrelation ee
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 ee
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 groundstate
orrelations due to the presen
e of an extra ele
tron require a larger
basis set. Ea
h of these two, partially
an
eling ee
ts is estimated to amount to band gap
orre
tions on the order of 12 eV based on mole
ular
al
ulations [157, 158, 159.
Lo
al proje
tor methods determine groundstate 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
tronhole pairs { than RPAbased approa
hes. In
ontrast to RPAbased GWA
al
ulations whose fundamental ex
itations are nonintera
ting
ele
tronhole pairs and plasmons, GWA
al
ulations based on a des
ription of s
reening in the
timedependent HartreeFo
k approximation in
lude the shortrange, 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 BetheSalpeter equation [154, 155, 156. The inverse diele
tri
matrix is given in terms of the densitydensity
orrelation fun
tion [165 and the latter
an be written as a twoparti
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 nonintera
ting ele
tronhole propagator
G0 (1; 10; 2; 20) = G(10 ; 20 )G(2; 1);
(76)
and I the irredu
ible ele
tronhole 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 BetheSalpeter 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 Wardidentitybased relation between the selfenergy and the vertex fun
tion is expe
ted to be better observed when the
irredu
ible polarizability is determined in the timedependent HartreeFo
k rather than the
timedependent Hartree approximation [156. This Wardidentitybased relation results from
harge
onservation. (ii) Hanke and
ollaborators suggest that the evaluation of the GWA
selfenergy with an intera
tion s
reened using the timedependent HartreeFo
k approximation is more appropriate than an evaluation of using an RPAs
reened intera
tion. The
hoi
e of s
reening in the timedependent HartreeFo
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 midseventies (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
mideighties.
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 dened by a \parametrized ThomasFermilike" approximation to the stati
selfenergy
[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 plasmonpole
model [98 (see Se
tion 8) and
orevalen
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 selfenergy 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 PariserParrPople 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 RPAbased 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 identied 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
ee
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 19701986. 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, rstprin
iples quasiparti
le
al
ulations were done
by Hybertsen and Louie [5 and in 1986 by Godby, S
hluter, and Sham [6. Firstprin
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 ee
ts in
the stati
COHSEX approximation and the negle
t of lo
aleld ee
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, dier 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.
HartreeFo
k
al
ulations oer a
onvenient singleparti
le basis for lowpolarizability
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
HartreeFo
k
al
ulations
on
entrate too mu
h density in the bonds.
Corevalen
e ex
hange and
orrelation potentials
an either be treated via ee
tive (e.g.,
orepolarization) 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
ombinationofatomi
orbitals basis [138, 139 or a basis set of lo
alized,
ontra
ted Gaussiantype orbitals [140, 141 { whi
h allow the analyti
evaluation of s
reenedex
hange twoele
tron
integrals { has been the method of
hoi
e in stati
COHSEX
al
ulations. Alternatively, uns
reened
ore
ore and
orevalen
e ex
hange potentials from Eq. (46) are taken into a
ount
in stati
COHSEX
al
ulations but selfenergy
ontributions due to
orevalen
e polarization
are negle
ted [133, 134, 135, 136.
Re
ent GWA
al
ulations [5, 6 extend earlier COHSEX work by using a nondiagonal,
frequen
ydependent [144, rstprin
iples diele
tri
matrix for the determination of quasiparti
le
orre
tions to the singleparti
le spe
trum. The treatment of
ore ele
trons is (i) at
LDA level [5, 6, (ii) impli
it via
orepolarization 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
(q; 0)xpq =
(67)
= pp :
0
(68)
= L(q)xpq
(69)
GG (q; ! ) =
ypq(G)ypq(G0 )
! 2 !p2(q)
(70)
(71)
These equations dene the Engel{Farid plasmonpole model. For future referen
e in the
determination of the selfenergy using the Engel{Farid plasmonpole model, we dene s
aled
plasmonpole eigenve
tors as
pq (G) =
4
1
ypq(G):
2!p(q) jq + Gj2
(72)
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 qve
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. Dene the following symmetrized, Hermitian diele
tri
matrix
"~GG (q; ! ) =
0
j q + G j " (q; ! );
jq + G0 j GG
(60)
(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 denition of the s
aled plasmonpole eigenve
tors as
pq (G)
pq (G)
j q + Gj
(63)
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 plasmonpole 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
highfrequen
y limits. With , , and L 1 , the inverse of the rstmoment 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 ee
tive masses [115. The ee
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 zerofrequen
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
tronhole ex
itations in plasmonpole models is justied for
energies
lose to the Fermi energy. Similar observations hold for semi
ondu
tors as dis
ussed
above.
The plasmonpole 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.
Plasmonpole models fail to give good des
riptions of systems whose imaginary selfenergy is
large [115. In parti
ular, lowlying 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
eband narrowing of about 0.3 eV in
Si
ompared to a plasmonpole model
al
ulation (
ompare the frequen
ydependent results
of Refs. [102, 103 with results using plasmonpole 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 plasmonpole model whi
h results in (i) N 2 plasmonpole parameters (N = size of the
diele
tri
matrix), (ii) a nontrivial extension of the model to systems without inversion
symmetry [121, and (iii) unphysi
al solutions with imaginary plasmonpole energies for some
odiagonal matrix elements. Rather than
on
entrating on the details of the HybertsenLouie plasmonpole model, we
onsider two alternative plasmonpole 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 selfenergy operator provided that appropriately
s
aled plasmonpole 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
plasmonpole 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 denes !gap .
To in
lude lo
aleld ee
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 LevineLouie potentials evaluated at r and r0 (see Eq. (56) below).
They evaluate the homogeneous LevineLouie s
reened potential
W LL (r
r0 )
= ["LL 1 (r
(54)
at the lo
al density determined by rs(r0 ) and use the LevineLouie gap parameter to ensure
orre
t longrange 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 HybertsenLouie diele
tri
matrix is given as the average over the
lo
al LevineLouie s
reening response at dierent points in the
rystal. The HybertsenLevineLouie 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. Plasmonpole 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 plasmonpole models approximate by a fun
tion
hara
terized by two parameters: the ee
tive strength and the ee
tive frequen
y of the
plasmon ex
itation. Together with the independentparti
le propagator (Eq. (15)), whose
frequen
y dependen
e is straightforward, plasmonpole 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.
Plasmonpole models give a good des
ription of both the lowenergy behavior of the
diele
tri
matrix { via reprodu
tion of the stati
limit { and the highenergy behavior of
20
onstant for small and mediumgap 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 LevineLouie model whi
h is introdu
ed below. However, in
ontrast to
the LevineLouie 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
, threedimensional, insulating ele
tron gas. Penn [109 uses the
Ehrenrei
hCohen 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 LevineLouie diele
tri
fun
tion [106 modies
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) fullls important sum rules su
h as the fsum rule, (iv ) has the
orre
t longwavelength
behavior, and (v ) negle
ts lo
aleld ee
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
(
!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
longwavelength 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 nonlo
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 dierent 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
aleld ee
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 selfenergy
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 independentparti
le ex
itations
for large q , (iii) redu
es to ThomasFermi s
reening for intermediate q , and (iv ) fullls important sum rules like the fsum rule. Lundqvist's [98 singleplasmonpolemodel 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
tronhole ex
itations
are negle
ted. In the
ase of the homogeneous ele
tron gas, Lundqvist [98, 100, 101 shows
that ele
tronhole ex
itations are of minor importan
e for the determination of the selfenergy
.
In inhomogeneous semi
ondu
tors su
h as Si quasiparti
le energies determined using
plasmonpole models (e.g., Ref. [42) dier 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 plasmonpole model
al
ulations [42). The ee
t
of parti
lehole 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 freeele
tron behavior at large q , (iii) des
ribes
a modied ThomasFermi s
reening at intermediate q , and (iv ) allows for the analyti
evaluation of the stati
Coulombhole
ontribution to the selfenergy. 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 ThomasFermi 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 rstprin
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
plasmonpole models, is determined from rstprin
iples using DFT rather than from model
diele
tri
matri
es.
This review fo
uses on the results of a
urate rstprin
iples
al
ulations of the selfenergy
sin
e these
al
ulations form a
onsistent framework for the dis
ussion of selfenergy ee
ts.
Results using model diele
tri
fun
tions will be used as supplementary material or in
ases
where no rstprin
iples
al
ulations exist.
Similar to model diele
tri
fun
tions, models for the selfenergy or the band gap
orre
tion are based on wellfounded physi
al insights into the ee
ts of
orrelation in solids
but their a
ura
y is often limited leading to semiquantitative results. A review of simplied
GWA
al
ulations based on models for either the diele
tri
fun
tion or the selfenergy
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
tronhole ex
itations whi
h fulll
the fsum rule at large re
ipro
al latti
e ve
tors where s
reening is less ee
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
lehole 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
uto ve
tor, the plasmon is the dominant ex
itation and exhausts the fsum
rule to more than 90% [93. Close to q
, the plasmon os
illator strength drops rapidly to
zero and parti
lehole ex
itations be
ome important. For large wave ve
tors (q 2kF )
the spe
trum
onverges towards the independentparti
le spe
trum sin
e s
reening be
omes
less and less ee
tive. A good model should therefore interpolate between the plasmon
(0 q q
) and the parti
lehole (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. Nonzero odiagonal matrix elements are needed to a
ount for
lo
aleld ee
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 dierent in a metal and
a semi
ondu
tor or insulator. In a metal, the Coulomb potential of a parti
le is s
reened
very ee
tively by the ele
tron gas, and the longrange Coulomb potential is turned into a
shortrange 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 singleparti
le Hamiltonian H^ 0 whose wave fun
tions and energies result in a good singleparti
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 HartreeFo
k. Although this strategy does not
orrespond to a
onsistent
determination of selfenergy
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. Manybody
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 selfenergy 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 denite matrix elements jhkjVm jkij2, whereas odiagonal 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
transitionmetal oxides [50, 54, 55, 91. The disadvantage of using an independentparti
le
Hamiltonian in the LDA is that density fun
tional theory is nonperturbative 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, HartreeFo
k
al
ulations provide a good singleparti
le basis only
for weaklypolarizable materials and are numeri
ally expensive due to the nonlo
ality of the
ex
hange kernel. HartreeFo
k Hamiltonians were used as independentparti
le Hamiltonians in the 70's and 80's to study selfenergy
orre
tions in rare earth and ioni
solids (see
Se
tion 9 a). Current uses of HartreeFo
k wave fun
tions and energies as input for GWA
al
ulations are limited to the study of transpolya
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
simplied 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 plasmonpole models. The
omputational
e
ien
y of model diele
tri
fun
tions and matri
es is oset 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 plasmonpole models (see Fig. 5), is less severe. As is dis
ussed
below and in
onne
tion with Table 21, Se
tion 18, plasmonpole 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
turnon 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 selfenergy equals the sum of the bare
oreex
hange potential, the s
reened
orepolarization potential, and the valen
e ele
tron
selfenergy, all of whi
h will be dened 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)
(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 identied 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 selfenergy of the
valen
e ele
trons (Gv Wv ).
A lo
al density approximation of the bare
oreex
hange and the s
reened
orepolarization
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 nonlo
al bare
oreex
hange and the s
reened, energydependent
orepolarization 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
orevalen
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
orevalen
e ex
hange and
orrelation breaks down and
leads to states that are systemati
ally too low in energy. Better treatments of
orevalen
e
ex
hange and
orrelation via (i) use of
orepolarization 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 SINGLEPARTICLE 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 singleparti
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 selfenergy is determined
15
Coulomb hole + s
reened ex
hange (COHSEX). The COHSEX approximation is a physi
ally motivated separation of the selfenergy into a Coulombhole (COH) and a s
reenedex
hange (SEX) part whose stati
limit (i) has been used extensively to
orre
t HartreeFo
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
aleld ee
ts on and the energy dependen
e of the selfenergy. 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
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 selfenergy
an then be written as the sum of a
Coulombhole
ontribution COH arising from the poles of the s
reened intera
tion and a
s
reenedex
hange
ontribution SEX arising from the poles of the Green fun
tion
Re = COH + SEX :
(40)
Using the independentparti
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 ))
(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 ee
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 selfenergy 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 veried 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);
(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
tronhole energies "m = EN;m EN;0 ,
and singleparti
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 singleparti
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
Energydependent
orrelations de
rease the HartreeFo
k band gap by raising the valen
eband energy and lowering the
ondu
tionband 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
tronhole energy "m , whi
h is on the s
ale of
the HartreeFo
k energy gap. Hen
e the polarization
ontribution to the selfenergy shifts
the valen
eband maximum upwards in energy. For the
ondu
tionband 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
tionband energy.
The
orrelation
ontribution to the selfenergy 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
selfenergy
X V (r)V (r)
m
m
C (r; r0; E = 0) (r r0 )
2r4 (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 selfenergy 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 timeordered 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 )
(31)
To des
ribe s
reening in solids in the timedependent Hartree or random phase approximation
(RPA), P is repla
ed by the independentparti
le polarizability P 0 whi
h
an be obtained
via the AdlerWiser formalism [80, 81, 82. If i (r) and "i are as in Eq. (15) and fi are the
orresponding Fermi fa
tors, the independentparti
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 independentparti
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
4
0
(34)
jq + Gj2 PGG (q; !):
To be
onsistent with the RPAbased 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
12
intera
tions, i.e., ladder diagrams,
auses the failures of RPAbased GWA
al
ulations. Improvements for absorption spe
tra
an be obtained by going beyond RPAbased GWA
al
ulations and in
luding vertex
orre
tions in the diele
tri
matrix and the selfenergy 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 manybody ee
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; ! ) =
(25)
"(r; r0 ; ! ) =
1
V
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 odiagonal elements "GG (q; ! ), G 6= G0 , des
ribe s
reening due to an inhomogeneous
density distribution, i.e., the lo
aleld ee
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 HartreeFo
k theory by the energydependent
orrelation
ontribution to the selfenergy (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) (
r0 ) (t)
i v (r
r00 )
(28)
(29)
(30)
r0 ) +
v (r
11
r00 )
(22)
(23)
(24)
The dynami
ally s
reened intera
tion approximation or GWA in prin
iple requires a self
onsistent determination of the singleparti
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 energydependent
orrelation ee
ts.
In parti
ular, we analyze in Se
tion 6 the selfenergy in terms of its bareex
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 energydependent
orrelation
ontribution results from W v . Dynami
ee
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 ae
ts
quasiparti
le energies (about a 20% ee
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 HartreeFo
k theory, whi
h is known to work well for systems su
h as
atoms or largebandgap, lowpolarizability solids like raregas solids and ioni
rystals [65.
In the latter
ase, the GWA roughly halves the HartreeFo
k gap and is
lose to experiment.
The energydependent
orrelation
orre
tion to HartreeFo
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
orelevel spe
tra in atoms, strong ele
tronele
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 shakeup peaks [76. The same observation holds for
nearlyfreeele
tron metals su
h as Na and Al [77.
The negle
t of vertex
orre
tions (see Se
tion 14) su
h as shortranged parti
leparti
le
10
quasiparti
le
al
ulations determine quasiparti
le energies via Eq. (17) on
e a suitable approximation for the selfenergy has been found.
5. THE HEDIN EQUATIONS AND THE GWA
In prin
iple, the exa
t selfenergy
an be obtained from a
losed set of integrodierential
equations { the Hedin equations [3, 4 { that in
onjun
tion with the Dyson equation link
the singleparti
le propagator G, the selfenergy , and the s
reened intera
tion W , to the
irredu
ible polarizability P and the vertex fun
tion whi
h will be dened now. Consider
the appli
ation of a small perturbation Vext to the manybody system. The irredu
ible
polarizability P is dened 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 selfenergy 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 denitions, 1+ = (r1 t1 + ), > 0 innitesimal, and v (1; 2) as bare Coulomb
intera
tion, Hedin's equations are
Z
(21)
G(r; r0 ; E ) = G0 (r; r0 ; E ) +
ZZ
(16)
(17)
(18)
The linear expansion of the selfenergy with respe
t to energy needed to derive the approximate relationship in Eq. (17) is well justied as will be detailed in Se
tion 11. Most
urrent
8
(12)
Ei
A(r; r0 ; E 0 ) 0
dE :
C E E0
(13)
The integral denes 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 innitesimally above the real E 0 axis for E 0 < and
innitesimally 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
(11)
the quasiparti
le life time, these additional ee
ts must be in
luded (see Refs. [26, 29, 30
and referen
es therein).
3. KOHNSHAM PARTICLES
All GWA
al
ulations start from a suitably
hosen oneparti
le Hamiltonian whose eigenfun
tions and eigenvalues are used to
onstru
t the singleparti
le propagator G, the s
reened
intera
tion W , and the selfenergy 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 groundstate
properties and, in parti
ular, the groundstate 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 groundstate 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 nonlo
al independentparti
le Hamiltonian su
h as HartreeFo
k (see Se
tion 7).
The KohnSham formulation of density fun
tional theory [34 maps the problem of N
intera
ting ele
trons onto a system of N nonintera
ting,
titious parti
les { the KohnSham parti
les { whi
h move in an ee
tive potential VKS . The KohnSham potential VKS
is
onstru
ted to ensure that the groundstate density of the nonintera
ting,
titious system
equals the groundstate 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 KohnSham Hamiltonian.
With Vext and VH as dened earlier, the set of singleparti
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 groundstate density n0 (r). The ex
hange
orrelation
energy, whi
h
ontains all Coulomb
orrelation ee
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 KohnSham 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 identied 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 nonintera
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 identies 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 identiable in the spe
trum, and (ii) is less
than unity sin
e A(E ) is positive denite 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 denition 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 initialstate (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 simplied 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 singleparti
le
spe
tral fun
tion. The intrinsi
photoemission spe
trum, i.e., the photoemission spe
trum
that takes only manyele
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 ee
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 dieren
e between the quasiparti
le and the bare parti
le is usually des
ribed
by the selfenergy [16, whi
h must a
ount for all ex
hange and
orrelation ee
ts beyond
the Hartree approximation. The selfenergy is a nonlo
al, energydependent, and in general
nonHermitian operator, whose properties will be dis
ussed in more detail in Se
tions 10
and 11. An exa
t determination of the selfenergy for real systems is not possible, sin
e it
ontains all the
omplexities of the manybody system. Instead, pra
ti
al approximations to
the selfenergy { 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 dene 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 singleparti
le operators su
h as the density and the total energy of a manybody
system are determined by the singleparti
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
singleparti
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,
timeordering operator, the singleparti
le Green fun
tion is dened 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 manybody
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 groundstate 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 selfenergy and vertex diagrams beyond
the random phase approximation. Mahan and Plummer [11 dis
uss manybody ee
ts in
photoemission spe
tra of simple spbonded 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
alorbital 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 planewave basis. We
ompare
all published rstprin
iples GWA
al
ulations for ve prototypi
al semi
ondu
tors (Si, Ge,
GaAs, SiC, GaN) and show that dieren
es between published quasiparti
le
al
ulations
for the lowest
ondu
tionband 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 realspa
e/imaginarytime 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, denes 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
itedstate 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
Denition 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 ee
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 oneparti
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.
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 manyele
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 singleparti
le Green fun
tion G, whose
exa
t determination requires
omplete knowledge of the quasiparti
le selfenergy [2. The
selfenergy is a nonHermitian, energydependent, and nonlo
al operator that des
ribes
ex
hange and
orrelation ee
ts beyond the Hartree approximation.
A determination of the selfenergy
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 selfenergy 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 mideighties was
the approa
h applied to larges
ale, numeri
al ele
troni
stru
ture
al
ulations [5, 6. The
resulting abinitio 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 selfenergy. Godby [9 reviews quasiparti
le
al
ulations for jellium, simple metals, and semi
ondu
tors. Mahan [10 examines dierent
1
21. SURFACES
22. DEFECTS
23. PRESSURE
24. EXCITONS
25. ATOMS AND MOLECULES
a. Atoms
b. Mole
ules
V. Metals
26. BULK
a. Corevalen
e ex
hange
b. Alkali metals
. d and f ele
tron metals
27. CLUSTERS
28. SURFACES
2. QUASIPARTICLES
3. KOHNSHAM PARTICLES
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