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Coulomb potential improves the prediction for the energy TABLE I. Positions of the atoms xᠬ ⫽ ␣ a⫹  b⫹ ␥ c inside the
gap without, however, achieving satisfactory agreement for primitive unit cell of ␣ -Fe2 O3 with respect to the basis vectors
other physical properties. In the latter two studies no relax- a,b,c of the primitive cell in terms of the two internal degrees of
ation of the atoms inside the supercell and also no variation freedom z Fe and x O . Experimental values are taken from Ref. 6.
of the volume of the cell was taken into account. Numbers in parentheses represent the uncertainty of the last digit.
In our study, we present results of a complete relaxation
process of cell size and atomic positions, in the framework of Atom Wyckoff ␣  ␥
symbol
DFT, based on the generalized gradient approximation
共GGA兲 and the projector augmented wave 共PAW兲 method. Fe 共c兲 z z z
We also performed GGA⫹U calculations to account for the 1/2⫺z 1/2⫺z 1/2⫺z
strong on-site Coulomb repulsion of the Fe d electrons. This 1/2⫹z 1/2⫹z 1/2⫹z
paper is organized as follows. In Sec. II we describe the 1⫺z 1⫺z 1⫺z
computational details, after that we briefly discuss in Sec. III z⫽0.10534(6)
how the on-site Coulomb interaction parameter U is intro- O 共e兲 x 1⫺x 0
duced in the framework of DFT. We present results of the
1⫺x 0 x
GGA calculations in Sec. IV, while results concerning
0 x 1⫺x
GGA⫹U will be given in Sec. V. Concluding remarks and
1/2⫺x 1/2⫹x 1/2
open key questions can be found in Sec. VI.
1/2⫹x 1/2 1/2⫺x
1/2 1/2⫺x 1/2⫹x
II. COMPUTATIONAL MODEL x⫽0.3056(9)
The calculations have been performed on the basis of
spin-polarized DFT34,35 with the Vienna ab initio simulation
package VASP.36 – 40 For the exchange-correlation functional, hematite is shown in Fig. 1, together with the rhombohedral
E xc , we chose a semi-local form proposed by Perdew and primitive cell used in our calculation. All iron atoms have an
Wang41 in 1991 using the GGA denoted hereby PW91. The equivalent octahedral environment. Therefore, electronic and
spin interpolation of Vosko et al.42 was used. The Kohn- magnetic properties will be the same at each iron site. The
Sham equations were solved via iterative matrix diagonaliza- octahedra built by oxygen atoms and centered by iron atoms
tion based on the minimization of the norm of the residual are slightly rotated against each other. We note that there are
vector to each eigenstate and optimized charge- and spin- two types of pairs of Fe atoms, which are characterized by a
mixing routines.43– 45 short Fe-Fe distance 共type A兲 and by a larger distance 共type
A number of eight valence electrons for each Fe atom B兲 along the hexagonal axis. There are two internal degrees
(3d 7 4s 1 ) and six valence electrons for each O atom of freedom, commonly named z Fe and x O , by which the
(2s 2 2p 4 ) were taken into account. The remaining 共core兲 positions of the atoms inside the primitive cell can be de-
electrons together with the nuclei were described by pseudo- scribed 共see Table I兲. We have relaxed the positions of the
potentials in the framework of the PAW method proposed by
Blöchl46 and adapted by Kresse and Joubert.36
The one-electron Kohn-Sham wavefunctions as well as
the charge density were expanded in a plane-wave basis set.
The results reported in this paper correspond to an energy
cutoff of 550 eV. It was checked that increasing the cutoff to
800 eV did not change total energies by more than 3 meV/
atom. Energy differences were affected by less than 0.3
meV/atom. For the calculation of total energies, the integra-
tion over the Brillouin zone was performed with a mesh of
8⫻8⫻8 k points generated by following the scheme of
Monkhorst and Pack.47 The DOS have been calculated with a
16⫻16⫻16 k point mesh.
An increase to 20⫻20⫻20 k points did not lead to any
visible change in the total DOS. The integration over the
irreducible part of the Brillouin zone was carried out using
the linear tetrahedron method with Blöchl corrections. The FIG. 1. 共Color online兲 Hexagonal unit cell of ␣ -Fe2 O3 共left兲
relaxation of the crystalline structure was performed using a together with the rhombohedral primitive cell 共right兲. Blue spheres
Gaussian-smearing approach with a width of 0.2 eV to speed represent Fe atoms, red spheres display the O atoms. The bilayer
up convergence. Pressure and bulk modulus were derived structure for the Fe atoms is clearly visible. Along the 关111兴 axis
from the calculated pressure-volume relation by fitting the there are two sorts of pairs of Fe atoms, one 共denoted as type A兲
data to a Murnaghan equation of state.48 with a short and one 共type B兲 with a larger Fe-Fe distance. The O
All calculations were carried out under rhombohedral atoms form close-packed basal planes, each Fe atom is coordinated
symmetry constraints. The complete hexagonal unit cell of octahedrally by six O atoms.
165107-2
FIRST-PRINCIPLES CALCULATION OF THE . . . PHYSICAL REVIEW B 69, 165107 共2004兲
TABLE II. Experimentally derived structural parameters for pancy matrix ( ) 2 ⫽ imposed by the second term in Eq.
␣ -Fe2 O3 taken from Ref. 1 共top兲 and Ref. 7 共bottom兲. Distances are 共3兲. For U⬎J, the term is positive definite, since the eigen-
given in Å. values ⑀ i of the on-site occupancy matrix are either 0 or 1,
c a c/a Fe-Fe 共A兲 Fe-Fe 共B兲
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G. ROLLMANN, A. ROHRBACH, P. ENTEL, AND J. HAFNER PHYSICAL REVIEW B 69, 165107 共2004兲
TABLE III. Order of the magnetic states at experimental volume, 10.06 Å3 /atom. Energies are in meV/共Fe atom兲, magnetic moments are
in ( B /Fe atom兲, and distances are in Å 共where NM stands for nonmagnetic兲.
Magnetic state Functional Reference Energy Magnetic moment c/a ratio Fe-Fe 共A兲 Fe-Fe 共B兲
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FIRST-PRINCIPLES CALCULATION OF THE . . . PHYSICAL REVIEW B 69, 165107 共2004兲
TABLE IV. Ground-state parameters for the different magnetic states. Volumes V 0 are in Å3 /atom, magnetic moments are in B /Fe
atom, distances are in Å, and bulk moduli B 0 are in GPa.
⫹⫺⫹⫺, ⫹⫺⫺⫹, and ⫹⫹⫹⫹ solutions, respectively. However, it must be emphasized that the experimental value
Related to this are kinks in the energy vs volume curves. of the bulk modulus is subject to considerable uncertainty.
These HS-LS transitions are more pronounced for the AF Sato and Akimoto’s value of 231 GPa is derived by a fit over
states compared to the FM solution, resulting in two clearly a very small pressure range of p⬍3 GPa, whereas a fit to
visible minima at least in the AF ⫹⫺⫹⫺ and ⫹⫺⫺⫹ pressures up to 10 GPa leads to B 0 ⬃178 GPa closer to our
energy curves. In the LS phases, the magnetic moments de- calculated value. The most recent result of Rozenberg et al.20
crease linearly with volume for the AF states, but stay almost is obtained by arbitrarily setting the pressure derivative B 0⬘
constant around 1 B for the FM state. For very low volumes ⫽⌬B 0 /⌬p in the Murnaghan fit to B 0⬘ ⫽4.
we did not succeed in stabilizing a LS AF ⫹⫺⫹⫺ phase.
The calculated bulk modulus for the FM state is consid-
Below 7.6 Å3 we observe the collapse of the AF ⫹⫺⫹⫺
erably larger, which is due to the fact that it has been evalu-
solution and obtain the NM state as the most stable solution.
ated for a lower volume and coincides well with the experi-
We note that at low pressure the AF solutions are much
more stable than the FM and the NM solutions. This is re- mental result that with increasing pressure hematite is
lated to the strong superexchange interaction mediated by the becoming harder. This can be observed directly when com-
O atoms. But we also note that at low volumes the FM so- paring the bulk moduli for the HS and LS solutions of the AF
lution is slightly lower in energy than the AF ⫹⫹⫺⫺ phase ⫹⫺⫹⫺ and the AF ⫹⫺⫺⫹ phases.
共although the energy difference is rather small, e.g., 2.5 Common to all magnetic states 共and the experimental
meV/atom for a volume of 8.46 Å3 /atom, but this is not of finding兲 is the dependence of the magnetic moment of the Fe
importance for the further discussion兲, corresponding to a atoms and the parameter z Fe on the volume. For volumes of
FM ground state at high pressures. By placing a common more than 10 Å3 /atom the moments are larger than 3 B /Fe
tangent to the FM and the AF ⫹⫹⫺⫺ curves, we obtain a atom and z Fe is greater than 0.103. This results in a differ-
value for the pressure, for which a HS-LS AF-FM transition ence between Fe-Fe 共A兲 and Fe-Fe 共B兲 distances of about
will occur, of 14 GPa. The corresponding volume reduction 1.0–1.1 Å. For volumes below 9 Å3 /atom the moments are
is 10.5%. As the rhombohedral corundum-type structure has smaller than 1.5 B /Fe atom and z Fe is less than 0.098, lead-
been reported to be the stable phase of ␣ -Fe2 O3 in the 0–50 ing to differences in Fe-Fe distances of more than 1.5 Å. We
GPa regime, we conclude that this transition is an artifact of conclude that the volume reduction seems to result in an
the simulation method, namely, the DFT in combination with increase of Fe-Fe 共B兲 distances and a strong decrease of
the GGA. It will be shown that when the GGA⫹U formal- Fe-Fe 共A兲 distances. In contrast to that a clear trend is not
ism is applied, the observed transition is shifted to higher visible for the parameter x O and the c/a ratio.
pressures with increasing U and eventually disappears for As not only the volume, but also the magnetic order de-
large values of U. termine the structural parameters, we now stick to the experi-
We have calculated structural parameters for each state by mentally observed AF ⫹⫹⫺⫺ state to examine further the
fitting the data in the volume regions corresponding to local dependence of crystalline structure of ␣ -Fe2 O3 on pressure.
minima of the energy curves to a third-order Birch- Figure 3 illustrates the dependence of the c/a ratio, the in-
Murnaghan equation of state 共Ref. 54兲. The results are given ternal degrees of freedom z Fe and x O , and the Fe-Fe and
in Table IV. For two of the AF curves, structural parameters Fe-O distances on pressure for the AF ⫹⫹⫺⫺ phase. For
were calculated for both HS and LS phases. The equilibrium comparison, experimental data from Ref. 19 is included. The
volume for the magnetic ground state agrees well with the straight solid lines mark the pressure of 14 GPa at which the
experimental value,7 although the corresponding magnetic AF-FM HS-LS transition takes place in our simulation. Up
moment is too low. This is probably due to the overestima- to that value, the structural parameters from our simulation
tion of hybridization of Fe 3d and O 2p states in conven- change almost linearly with pressure. Around p c , a rapid
tional GGA. We also obtain a value for the bulk modulus change, especially in c/a ratio, is observed, followed by
which is lower than the values found experimentally.6,7,20 nearly perfect linear behavior above p c . The HS-LS transi-
165107-5
G. ROLLMANN, A. ROHRBACH, P. ENTEL, AND J. HAFNER PHYSICAL REVIEW B 69, 165107 共2004兲
B. Electronic structure
In order to analyze electronic properties of ␣ -Fe2 O3 we
calculated the DOS for all energy minima of the curves. In
Fig. 4 the partial DOS of Fe 3d (t 2g and e g ) and O 2p states
for the AF ⫹⫹⫺⫺ solution at experimental volume are
shown. A band gap of ⬇0.3 eV is clearly visible. As is usu-
ally the case for calculations based on DFT, this is much
smaller 共by about a factor of 6兲 than the experimental value
of 2.0 eV 共Ref. 55兲. For comparison, Punkkinen and
co-workers,33 who applied GGA in combination with the lin- FIG. 4. Orbital projected DOS 共PDOS兲 for the AF ⫹⫹⫺⫺
ear muffin-tin orbital 共LMTO兲 method in atomic-sphere ap- solution of Fe2 O3 , calculated within the GGA. The left 共right兲 panel
proximation 共ASA兲, obtained a value of 0.51 eV for the band shows spin-up 共spin-down兲 Fe e g , Fe t 2g , and O 2p projections.
gap, Sandratskii et al.32 got a value of 0.75 eV by using The orbitals are projected onto Wigner-Seitz spheres.
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FIRST-PRINCIPLES CALCULATION OF THE . . . PHYSICAL REVIEW B 69, 165107 共2004兲
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G. ROLLMANN, A. ROHRBACH, P. ENTEL, AND J. HAFNER PHYSICAL REVIEW B 69, 165107 共2004兲
experiment shows O 2p domination and therefore a charge- FIG. 7. Volume dependence of the free energy and the mag-
netic moment for GGA⫹U with U⫽1 共GGA兲, 4, and 7 eV. The
transfer type of band gap. Furthermore, the Fe 3d band en-
tangent on the GGA curves mark the phase transition from the
ergies from GGA are not in agreement with experimental
AF ⫹⫹⫺⫺ to the ferromagnetic phase for U⫽1 eV.
valence-band spectra and conduction-band spectra. GGA
also predicts ␣ -Fe2 O3 to undergo a magnetic phase transition
at ⬃ 14 GPa, which is not found in experiment. On the other behavior of the volume with varying U. The c/a ratio
hand, the GGA prediction of the equilibrium volume agrees slightly decreases from c/a⬃2.77 for GGA at an equilibrium
quite well with experimental data. volume of 10.00 Å3 /atom to ⬃2.73 for GGA⫹U with U
The inaccurate results for some of the ground-state prop- ⫽5 eV at an equilibrium volume of 10.30 Å3 /atom and to
erties of hematite obtained with GGA are attributable to the ⬃2.72 for GGA⫹U with U⫽7 eV at an equilibrium volume
improper description of the on-site Coulomb repulsion be- of 10.24 Å3 /atom. Agreement with the experimental value of
tween the localized Fe 3d electrons. The DFT⫹U method by c/a⫽2.73 is again best for U⬃5 eV. Concerning the bulk
explicitly taking into account the on-site Coulomb repulsion modulus, we can observe an increase from the GGA value of
improves the predictions for the band gap, band energies, 173 GPa at an equilibrium volume of 10.00 Å3 /atom to the
and magnetic moments. Figure 6 illustrates the dependence GGA⫹U value for U⫽4 eV with 177.4 GPa at an equilib-
of equilibrium volume, Fe-Fe 共A兲 distance, magnetic mo-
rium volume of 10.30 Å3 /atom. For U⫽7 eV, the bulk
ments, and band gap on U. The parameter J was kept con-
modulus increases to 178.8 GPa at an equilibrium volume of
stant at 1 eV for all calculations.
10.24 Å3 /atom. The bulk modulus remains too small com-
GGA⫹U stabilizes the high-spin AF ⫹⫹⫺⫺ ground
state as in the GGA limit, U⫽1 eV. The experimental mag- pared to experiment6,7,20 even for large U parameters.
netic moment is reached only for U⫽8 –9 eV, whereas for Figure 7 shows the volume dependence of the total energy
the band gap full agreement is obtained for moderate values and the magnetic moment for U⫽1, 4, and 6 eV.
of U⬃5 eV. The results for magnetic moment and band gap For the GGA limit, U⫽1 eV, the transitions between the
are in good agreement with former GGA⫹U calculations LS and HS AF ⫹⫹⫺⫺ phases are clearly visible, but the
using the tight-binding LMTO-ASA method56 –58 of Punkki- HS solution is the stable one. Near a volume of
nen et al.,33 using the experimental structure. The choice of ⬃9.3 Å3 /atom, the LS FM phase becomes energetically fa-
an appropriate value for U is the same in both cases. The vorable. The observed pressure at the phase transition is
volume shows only a weak dependence on U. With increas- ⬃14 GPa. The LS FM phase at this pressure is half metallic,
ing U, it increases first until at U⫽5 eV a maximum value whereas the HS AF ⫹⫹⫺⫺ phase is weakly insulating with
of ⬃10.3 Å3 is reached and then decreases slightly for larger a band gap of ⬃0.5 eV. At U⫽4 eV, the AF ⫹⫹⫺⫺ HS
U values. The agreement with experiment is reasonable to LS phase transition no longer occurs, the FM HS to LS
throughout the entire U range. The Fe-Fe 共A兲 distance phase transition happens at ⬃8.5 Å3 /atom.
reaches its maximum value of ⬃2.95 Å already for U The U⫽7 eV case does not show any significant changes
⫽2 eV and decreases slightly when further increasing U. concerning phase transition and energetical stability com-
The agreement with the experimental value of ⬃2.896 Å pared to the U⫽4 eV case. Figure 8 shows the pressure
共Ref. 7兲 is best for U⫽5 eV. The Fe-Fe distance reflects the dependence of the c/a ratio, the internal parameters x, z, and
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FIRST-PRINCIPLES CALCULATION OF THE . . . PHYSICAL REVIEW B 69, 165107 共2004兲
B. Electronic structure
The spin-polarized and orbital projected DOS, calculated
in the GGA⫹U with U⫽4 eV is shown in Fig. 9. The on-
site Coulomb repulsion is found to have a profound influence
on the electronic spectrum. The occupied Fe 3d states are
shifted to higher binding energies, breaking the strong Fe
3d –O 2p hybridization characteristic for the electronic
structure calculated in the GGA. The occupied states close to
the Fermi energy are now entirely oxygen dominated, with
only a small admixture of Fe t 2g minority states. The empty
Fe 3d minority states are up shifted, increasing the width of
the gap. In contrast to the GGA predicting hematite to be an
insulator with a very narrow gap created by the exchange
splitting in the Fe 3d band, GGA⫹U with U⫽4 eV leads to
a charge-transfer type O 2p –Fe 3d gap of nearly 2 eV, in
agreement with experiment.
Figure 10 shows the calculated intensities of the photo-
emission 共PES兲 and inverse photoemission 共IPES兲 spectra,
compared with the experimental results of Fujimori et al.10
and Ciccacci et al.12 In spite of the fact that the one-particle
DFT eigenvalues have no direct physical meaning, it is well
established that calculated DOS and experimental PES can
be compared on a qualitative basis, especially when the
FIG. 8. Variation of the c/a ratio 共upper panel兲, the internal bands are very broad. In this sense the theoretical spectra are
parameters x O and z Fe 共middle兲, and the Fe-Fe distances 共lower approximated by the sum over the partial DOS, weighted
panel兲 with pressure for GGA and GGA⫹U with U⫽4 eV, to- with the partial photoionization cross section of Yeh and
gether with experimental results taken from Ref. 20. Lindau,59 folded with a Gaussian to simulate the effect of a
finite instrumental resolution. The analysis of the PES and
the Fe-Fe distances for GGA and GGA⫹U with U⫽4 eV, IPES spectra confirms the conclusion that at least moderately
together with experimental results taken from Rozenberg strong on-site interactions must be included to achieve a cor-
et al.20 rect description of the electronic structure of hematite. In the
It can be seen that experimentally there is no HS to LS GGA limit and even with U⫽2 eV, the narrow gap at the
phase transition for the stable AF ⫹⫹⫺⫺ phase. Therefore, Fermi level is completely covered by the finite resolution of
only the calculations with U⭓4 eV give a proper qualitative the spectra, the lower edge of the valence band is found at
description for the behavior of ␣ -Fe2 O3 under pressure. Ex- too low binding energies, and the dominant peak in the con-
perimentally, Rozenberg et al.20 have shown that ␣ -Fe2 O3 duction band is too close to the Fermi level. U⫽4 eV leads
undergoes a structural phase transition at a pressure of to reasonable agreement with experiment. The structure in
⬃50 GPa, but they did not see a phase transition from the the valence band with separated peaks at E⬃⫺7 eV domi-
AF ⫹⫹⫺⫺ phase to the FM phase for pressures up to 50 nated by Fe 3d states and at E⬃⫺3 eV dominated by O 2p
GPa. In this pressure range the calculated structural param- states is more pronounced than in experiment. This is a con-
eters show very good agreement with experiment. sequence of the fact that the on-site Coulomb potential acts
A symmetry analysis of the relaxed structures of the AF only on the Fe 3d states, leading to a reduction of the Fe-O
⫹⫹⫺⫺ order at low volumes has shown that for the GGA hybridization which is too strong. However, GGA⫹U with
case, the structure of the bulk undergoes a slight distortion U⫽4 eV leads undoubtedly to a marked improvement of the
into a structure with monoclinic symmetry at a volume of calculated electronic structure.
⬃6.6 Å3 /atom, corresponding to a pressure of ⭓100 GPa. Punkkinen et al.33 found a value of U⫽2 eV as an opti-
For U⫽4 eV, the structural distortion happens at a volume mum from their DOS interpretation. They remarked that al-
of ⬃7.3 Å3 /atom, corresponding to a pressure of ready for U⫽3.5 eV, the occupied Fe 3d states are shifted
165107-9
G. ROLLMANN, A. ROHRBACH, P. ENTEL, AND J. HAFNER PHYSICAL REVIEW B 69, 165107 共2004兲
too much towards lower energies. The reason for the dis-
agreement with our conclusions is twofold.
共i兲 Punkkinen et al. used a different version of the DFT⫹
U Hamiltonian which is not rotationally invariant.
共ii兲 There are significant differences already at the GGA
level. As no information on the magnetic structure is given in
the paper, the possibility that the calculation refer to a differ-
ent antiferromagnetic configuration cannot be excluded.
VII. CONCLUSIONS
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FIRST-PRINCIPLES CALCULATION OF THE . . . PHYSICAL REVIEW B 69, 165107 共2004兲
which best overall agreement is achieved. change in the adsorption geometry 共tilted vs perpendicular兲,
An important result of this study is the profound change markedly improving agreement with experiment. Although
in the semiconducting gap from a d-d exchange gap to an O the on-site Coulomb repulsion is stronger in NiO than in
2 p –Fe 3d charge-transfer gap, paralleled by the change of Fe2 O3 (U⫽6.3 eV vs U⫽4 eV), we expect similar effects
the frontier orbitals 共the highest occupied valence states兲 in hematite as well. Due to the much more complex crystal
from strongly hybridized O 2p –Fe 3d to almost pure O 2p structure, even the surface termination could be influenced.
character. As the frontier orbitals determine the chemical re-
activity of the surface of a material, we expect a non-
negligible influence of the on-site Coulomb repulsions on the ACKNOWLEDGMENTS
stable surface termination and on the adsorption of atoms
and molecules on hematite surfaces. Recent work by two of Work at the University of Duisburg has been supported by
us60 on the adsorption of small molecules such as CO on the SFB 445 ‘‘Nanoparticles from the Gas phase: Formation,
NiO共100兲 has demonstrated that the strong correlation effects Structure, Properties’’; work at the University of Vienna was
present in these materials lead to a reduction of the adsorp- supported by the Austrian Science Funds through the Science
tion energy by more than a factor of 2 and a qualitative College ‘‘Computational Materials Science.’’
1
L. Pauling and S.B. Hendricks, J. Am. Chem. Soc. 47, 781 23
F. Bo” dker, M.F. Hansen, C.B. Koch, K. Lefmann, and S. Mo” rup,
共1925兲. Phys. Rev. B 61, 6826 共2000兲.
2
C.W. Searle and G.W. Dean, Phys. Rev. B 1, 4337 共1970兲. 24
M.D. Towler, N.L. Allan, N.M. Harrison, V.R. Saunders, W.C.
3
L.M. Levinson, Phys. Rev. B 3, 3965 共1971兲. Mackrodt, and E. Aprà, Phys. Rev. B 50, 5041 共1994兲.
4
H. Chow and F. Keffer, Phys. Rev. B 10, 243 共1974兲. 25
Z. Fang, I.V. Solovyev, H. Sawada, and K. Terakura, Phys. Rev. B
5
L.M. Sandratskii and J. Kübler, Europhys. Lett. 33, 447 共1996兲. 59, 762 共1999兲.
6
Y. Sato and S. Akimoto, J. Appl. Phys. 50, 5285 共1979兲. 26
O. Bengone, M. Alouani, P. Blöchl, and J. Hugel, Phys. Rev. B
7
L.W. Finger and R.M. Hazen, J. Appl. Phys. 51, 5362 共1980兲. 62, 16 392 共2000兲.
8 27
T. Yagi and S. Akimoto, High Pressure Research in Geophysics S.L. Dudarev, G.A. Botton, S.Y. Savrasov, C.J. Humphreys, and
共Kluwer Academic, Tokyo, 1982兲. A.P. Sutton, Phys. Rev. B 57, 1505 共1998兲.
9
Suzuki, T. Yagi, A. Akimoto, A. Ito, S. Morimoto, and S. Syono, 28
M.R. Castell, S.L. Dudarev, G.A.D. Briggs, and A.P. Sutton,
Solid State Physics Under Pressure 共KTK Scientific, Tokyo, Phys. Rev. B 59, 7342 共1999兲.
1985兲. 29
D. Ködderitzsch, W. Hergert, W.M. Temmerman, Z. Szotek, A.
10
A. Fujimori, M. Saeki, N. Kimizuka, M. Taniguchi, and S. Suga,
Ernst, and H. Winter, Phys. Rev. B 66, 064434 共2002兲.
Phys. Rev. B 34, 7318 共1989兲. 30
G. Pacchioni, Surf. Rev. Lett. 7, 277 共2000兲.
11
R.J. Lad and V.E. Henrich, Phys. Rev. B 39, 13 478 共1989兲. 31
12 M. Catti, G. Valerio, and R. Dovesi, Phys. Rev. B 51, 7441
F. Ciccacci, L. Braicovich, E. Puppin, and E. Vescovo, Phys. Rev.
共1995兲.
B 44, 10 444 共1991兲. 32
13 L.M. Sandratskii, M. Uhl, and J. Kübler, J. Phys.: Condens. Mat-
J.S. Olsen, C.S.G. Cousins, L. Gerward, H. Jhans, and B.J. Shel-
ter 8, 983 共1996兲.
don, Phys. Scr. 43, 327 共1991兲. 33
14
G. Dräger, W. Czolbe, and J.A. Leiro, Phys. Rev. B 45, 8283 M.P.J. Punkkinen, K. Kokko, W. Hergert, and I.J. Väyrynen, J.
共1992兲. Phys.: Condens. Matter 11, 2341 共1999兲.
15
D.L.A. de Faria, S.V. Silva, and M.T. de Oliveira, J. Raman Spec-
34
P. Hohenberg and W. Kohn, Phys. Rev. 136, B864 共1964兲.
trosc. 28, 873 共1997兲.
35
W. Kohn and L.J. Sham, Phys. Rev. 140, A1133 共1965兲.
16
T. Uozumi, K. Okada, A. Kotani, R. Zimmermann, P. Steiner, S.
36
G. Kresse and D. Joubert, Phys. Rev. B 59, 1758 共1999兲.
Hüfner, Y. Tezuka, and S. Shin, J. Electron Spectrosc. Relat.
37
G. Kresse and J. Hafner, Phys. Rev. B 47, 558 共1993兲.
Phenom. 83, 9 共1997兲.
38
G. Kresse and J. Hafner, Phys. Rev. B 49, 14 251 共1994兲.
17
M.-Z. Dang, D.G. Rancourt, J.E. Dutrizac, G. Lamarche, and R. 39
G. Kresse and J. Furthmüller, Phys. Rev. B 54, 11 169 共1996兲.
Provencher, Hyperfine Interact. 117, 271 共1998兲. 40
G. Kresse and J. Furthmüller, Comput. Mater. Sci. 6, 15 共1996兲.
18
J. Badro, V.V. Struzhkin, J. Shu, R.J. Hemley, H.-K. Mao, C.-C. 41
J.P. Perdew and Y. Wang, Phys. Rev. B 45, 13 244 共1992兲.
Kao, J.-P. Rueff, and G. Shen, Phys. Rev. Lett. 83, 4101 共1999兲. 42
S.H. Vosko, L. Wilk, and M. Nusair, Can. J. Phys. 58, 1200
19
M.P. Pasternak, G.K. Rozenberg, G.Y. Machavariani, O. Naaman, 共1980兲.
R.D. Taylor, and R. Jeanloz, Phys. Rev. Lett. 82, 4663 共1999兲. 43
D.M. Wood and A. Zunger, J. Phys. A 18, 1343 共1985兲.
20
G.K. Rozenberg, L.S. Dubrovinsky, M.P. Pasternak, O. Naaman, 44
D.D. Johnson, Phys. Rev. B 38, 12 807 共1988兲.
T. LeBihan, and R. Ahuja, Phys. Rev. B 65, 064112 共2002兲. 45
P. Pulay, Chem. Phys. Lett. 73, 393 共1980兲.
21
J. Badro, G. Fiquet, V.V. Struzhkin, M. Somayazulu, H.-K. Mao, 46
P.E. Blöchl, Phys. Rev. B 50, 17 953 共1994兲.
G. Shen, and T. LeBihan, Phys. Rev. Lett. 89, 205504 共2002兲. 47
H. Monkhorst and J.D. Pack, Phys. Rev. B 13, 5188 共1976兲.
22
K. Lefmann, F. Bo” dker, M.F. Hansen, H. Vázquez, N.B. Chris- 48
F.D. Murnaghan, Proc. Natl. Acad. Sci. U.S.A. 30, 244 共1944兲.
tensen, P.-A. Lindgård, K.N. Clausen, and S. Mo” rup, Eur. Phys. 49
A. Kotani and T. Yamazaki, Prog. Theor. Phys. Suppl. 108, 117
J. D 9, 491 共1999兲. 共1992兲.
165107-11
G. ROLLMANN, A. ROHRBACH, P. ENTEL, AND J. HAFNER PHYSICAL REVIEW B 69, 165107 共2004兲
50
I.V. Solovyev, P.H. Dederichs, and V.I. Anisimov, Phys. Rev. B 405.
50, 16 861 共1994兲. 55
S. Mochizuki, Phys. Status Solidi A 41, 591 共1977兲.
51
A.I. Liechtenstein, V.I. Anisimov, and J. Zaanen, Phys. Rev. B 52, 56
O.K. Andersen, Phys. Rev. B 12, 3060 共1975兲.
R5467 共1995兲. 57
H. L. Skriver, The LMTO Method, Springer Series in Solid-State
52
A. Rohrbach, J. Hafner, and G. Kresse, J. Phys.: Condens. Matter Sciences Vol. 41 共Springer, Berlin, 1984兲.
15, 979 共2003兲. 58
O.K. Andersen and O. Jepsen, Phys. Rev. Lett. 53, 2571 共1984兲.
53
E. Kren, P. Szabo, and G. Konczos, Phys. Lett. 19, 103 共1965兲. 59
J.J. Yeh and I. Lindau, At. Data Nucl. Data Tables 32 共1985兲.
54
O. L. Anderson, Equations of State for Solids in Geophysics and 60
A. Rohrbach, J. Hafner, and G. Kresse 共unpublished兲.
Ceramic Science 共Oxford University Press, Oxford, 1995兲, p.
165107-12