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First-principles calculation of the structure and magnetic phases of hematite

First-principles calculation of the structure and magnetic phases of hematite

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G. Rollmann,1 A. Rohrbach,2 P. Entel,1 and J. Hafner2

1

Institut für Theoretische Physik, Universität Duisburg-Essen, Lotharstrasse 1, 47048 Duisburg, Germany

2

Institut für Materialphysik and Center for Computational Materials Science, Universität Wien, Sensengasse 8/12,

A-1090 Wien, Austria

共Received 20 June 2003; published 6 April 2004兲

Rhombohedral ␣ -Fe2 O3 has been studied by using density-functional theory 共DFT兲 and the generalized

gradient approximation 共GGA兲. For the chosen supercell all possible magnetic configurations have been taken

into account. We find an antiferromagnetic ground state at the experimental volume. This state is 388 meV/共Fe

atom兲 below the ferromagnetic solution. For the magnetic moments of the iron atoms we obtain 3.4 B , which

is about 1.5 B below the experimentally observed value. The insulating nature of ␣ -Fe2 O3 is reproduced, with

a band gap of 0.32 eV, compared to an experimental value of about 2.0 eV. Analysis of the density of states

confirms the strong hybridization between Fe 3d and O 2p states in ␣ -Fe2 O3 . When we consider lower

volumes, we observe a transition to a metallic, ferromagnetic low-spin phase, together with a structural

transition at a pressure of 14 GPa, which is not seen in experiment. In order to take into account the strong

on-site Coulomb interaction U present in Fe2 O3 we also performed DFT⫹U calculations. We find that with

increasing U the size of the band gap and the magnetic moments increase, while other quantities such as

equilibrium volume and Fe-Fe distances do not show a monotonic behavior. The transition observed in the

GGA calculations is shifted to higher pressures and eventually vanishes for high values of U. Best overall

agreement, also with respect to experimental photoemission and inverse photoemission spectra of hematite, is

achieved for U⫽4 eV. The strength of the on-site interactions is sufficient to change the character of the gap

from d-d to O-p-Fe-d.

torted corundum-type (Rh2 O3 -II) phase with a single Fe3⫹

Among the iron oxides, corundum-type ␣ -Fe2 O3 共hema- cation.

tite兲 is the most common on earth. At ambient conditions, it From a theoretical point of view, the study of hematite is

crystallizes in the rhombohedral corundum structure 共space very attractive because of the challenges it poses to theory.

group R3̄c), see Ref. 1. Below the Néel temperature, T N The Fe d electrons in Fe2 O3 are strongly correlated, so meth-

⫽955 K, ␣ -Fe2 O3 is an antiferromagnetic 共AF兲 insulator ods beyond ordinary density-functional theory 共DFT兲 in the

showing weak ferromagnetism above the Morin temperature, local spin-density approximation 共LSDA兲 are needed to cor-

rectly describe the system in terms of electronic and mag-

T M⫽260 K, due to a slight canting of the two sublattice

netic properties. As the rhombohedral primitive cell of hema-

magnetizations.2–5 Below T M , the direction of the magnetic

tite contains ten atoms 共compared to only two atoms in

moments is parallel to the 关111兴 axis of the hexagonal unit

simple transition-metal 共TM兲 oxides with the rocksalt struc-

cell. The localization of the iron 3d electrons due to the ture兲, considerable computational effort is required to obtain

strong on-site Coulomb repulsion results in a large splitting reasonable results concerning the crystalline, electronic, and

of the d bands and a band gap of 2 eV. As the upper edge of magnetic structures of hematite.

the valence band is dominated by oxygen p states, hematite This might be responsible for the fact that, in contrast to

is generally considered to be a charge-transfer rather than a studies of NiO, FeO, and similar TM monoxides, which have

Mott-Hubbard insulator. been studied extensively using ab initio methods,24 –30 there

There has been a considerable amount of experimental are only a few theoretical works4,5,16,31,32,33 concerning

work on hematite, regarding its structural, magnetic, and ␣ -Fe2 O3 . The Hartree-Fock 共HF兲 study of Catti et al.31 al-

electronic properties in bulk1–3,6 –21 as well as in ready achieves the correct order of magnetic states at experi-

nanoparticles.22,23 Especially the nature of the high-pressure mental volume, yielding an energy difference between anti-

共HP兲 transition of ␣ -Fe2 O3 has recently been discussed in ferromagnetic and ferromagnetic 共FM兲 alignments of the

detail.6 –9,13,19–21 At pressures around 50 GPa a shrinkage of spins of 37 meV/共Fe atom兲, although the obtained mixing of

the crystal volume of about 10% together with a collapse of oxygen 2p and iron 3d electrons is very weak. In addition,

the magnetic moments and a concurrent insulator-metal tran- the energy gap is grossly overestimated while the predicted

sition due to the breakdown of the d-d correlation has been bandwidth is too small. Sandratskii et al.32 studied ␣ -Fe2 O3

observed. This transition was found to be isostructural, but using conventional LSDA. They find an AF bilayer sequence

subsequent to a change in crystalline structure.21 For quite a for the Fe moments to be lowest in energy: 489 meV/共Fe

long time the HP phase of ␣ -Fe2 O3 was considered to be of atom兲 lower than the FM state. In a recent LDA⫹U study,

the orthorhombic perovskite type, containing Fe2⫹ and Fe4⫹ Punkkinen et al.33 concentrate on the density of states

sites in the same amount.7,8,9,13 Recently, Pasternak et al.19 共DOS兲. They find that even a modest value of the on-site

G. ROLLMANN, A. ROHRBACH, P. ENTEL, AND J. HAFNER PHYSICAL REVIEW B 69, 165107 共2004兲

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

⫺ ⫽ 兺i ⑀ i ⫺ 共 ⑀ i 兲 2 ⬎0,

13.747 5.035 2.730 2.896 3.977

where the sum on the right-hand side is over all eigenvalues

⑀ i of the on-site occupancy matrix . Hence the second

atoms in terms of these parameters, as well as the c/a ratio

term in Eq. 共3兲 can be interpreted as a positive definite pen-

of the supercell, by using the conjugate gradient method until

alty function driving the on-site occupancy matrices towards

the forces on each atom were below 5 meV/Å. Structural

idempotency, whose strength is parametrized by a single pa-

parameters of hematite derived experimentally at zero pres-

rameter (U⫺J). A larger (U⫺J) forces a stricter observance

sure by Pauling and Hendricks1 and Finger and Hazen7 are

of the on-site idempotency, achieved by lowering the one-

given in Table II. For DFT⫹U calculations, the version de-

electron potential locally for a particular metal d orbital and

scribed in the following section was used.

in turn reducing the hybridization with, e.g., O atoms. The

one-electron potential is given by the functional derivative of

III. DFT¿U METHOD the total energy with respect to the electron density, i.e., in a

The on-site Coulomb repulsion amongst the localized TM matrix representation,

3d electrons is not described very well in a spin-polarized

DFT treatment. A conceptually better method 共DFT⫹U)

consists of combining the DFT with a Hubbard-Hamiltonian,

thereby considering this Coulomb repulsion explicitly. In the

V i j ⫽

␦ E DFT⫹U

␦ i j

⫽

␦ E DFT

␦ i j

⫹ 共 U⫺J 兲 冋 1

2 ij 册

␦ ⫺ i j . 共4兲

based on a model Hamiltonian with the form49 It is recognized that filled d orbitals, which are localized on

one particular site, are moved to lower energies, by ⫺(U

U U⫺J ⫺J)/2, whereas empty d orbitals are raised to higher ener-

Ĥ⫽

2 兺 n̂ m n̂ m ⬘⫺ ⫹ 2 兺 n̂ m n̂ m ⬘ , 共1兲 gies by (U⫺J)/2. For the implementation of the DFT⫹U

⬘

m,m , m⫽m ⬘ ,

approach within VASP, see Ref. 52.

where n̂ m is the operator yielding the number of electrons

occupying an orbital with magnetic quantum number m and

IV. RESULTS AND DISCUSSION OF GGA CALCULATIONS

spin at a particular site.

The Coulomb repulsion is characterized by a spherically A. Crystal structure and magnetization

averaged Hubbard parameter U describing the energy re- The total energies per atom and magnetic moments of the

quired for adding an extra d electron to an Fe atom, U Fe atoms as a function of the volume per atom are displayed

⫽E(d n⫹1 )⫹E(d n⫺1 )⫺2E(d n ), and a parameter J repre- in Fig. 2. The curves belonging to different magnetic solu-

senting the screened exchange energy. While U depends on tions are indexed according to the orientation of the local

the spatial extension of the wave functions and on screening, spin density around the Fe atoms. As zero energy the global

J is an approximation of the Stoner exchange parameter and energy minimum was taken, corresponding to an AF ⫹⫹

almost constant J⬃1 eV 共see Ref. 50兲. The spin-polarized ⫺⫺ state, which means that Fe atoms belonging to type A

DFT⫹U energy functional is obtained by subtracting the pairs 共short distance, see Sec. II兲 have opposite magnetic

Mott-Hubbard contributions already existing in the DFT moment, while Fe atoms belonging to type B pairs 共larger

functional 共‘‘double-counting’’ contributions兲50 and after distance兲 have equal magnetic moments. Each point on every

some straightforward algebra one obtains curve represents the result obtained after full relaxation of

U⫺J the cell shape (c/a ratio兲, atomic positions 共under rhombo-

E DFT⫹U ⫽E DFT⫹

2 兺

m

共 n m ⫺n m

2

兲. 共2兲 hedral symmetry constraints兲, and magnetic moments for the

corresponding volume.

This form is not invariant under a unitary transformation of For a discussion we first draw our attention to the order of

the orbitals. However, when replacing the number operator states at experimental volume. Corresponding structural, en-

by the on-site density matrix i j of the d electrons, Lichten- ergetic, and magnetic properties of the different magnetic

stein et al.51 obtain a rotationally invariant energy functional, solutions for a volume of 10.06 Å3 are presented in Table III.

which in the present case is of the form The energy differences between the AF ⫹⫹⫺⫺ and the

other two AF states agree well with results of the LSDA

U⫺J calculation reported by Sandratskii and co-workers.32 The

E DFT⫹U ⫽E DFT⫹

2 兺 Tr关 ⫺ 兴 . 共3兲 total energy of the FM solution is comparable to the corre-

sponding value in the same publication, but considerably

This yields exactly the same energy as the DFT functional larger than the value found by Catti et al.31 within their HF

E DFT⫹U ⫽E DFT in the limit of an idempotent on-site occu- study. The nonmagnetic 共NM兲 solution is highest in energy.

165107-3

G. ROLLMANN, A. ROHRBACH, P. ENTEL, AND J. HAFNER PHYSICAL REVIEW B 69, 165107 共2004兲

2.8333. The unit cell of hematite is slightly shortened in c

direction with respect to this ideal cell, the experimentally

measured c/a ratio at zero pressure is 2.73 共Ref. 7兲. We find

that the calculated values for the c/a ratios for all three AF

states agree well with this number, while the c/a ratios for

the FM and the NM state are somewhat larger and closer to

the ideal value. The internal structural parameters 共and hence

the Fe-Fe distances兲 also show a pronounced dependence on

the magnetic configuration. For the stable AF ⫹⫹⫺⫺

phase, we note good agreement with experiment, in the other

magnetic configurations substantial differences are observed.

These effects are largest in the FM configuration where

smaller values of z and larger x parameters lead to a strongly

increased difference of the bond lengths in Fe-Fe 共A兲 and

Fe-Fe 共B兲 pairs. The contraction of the shortest Fe-Fe dis-

tances contributes to the quenching of the magnetic moments

in the FM phase.

When comparing our results to other theoretical work we

first note that we get the same order of states as Sandratskii

et al. But while the energy differences between the AF

phases are similar, we get the FM solution closer to the AF

states by 110 meV per Fe atom. From a calculation of the

total energy for the FM state at a volume of 10.06 Å3 per Fe

FIG. 2. Total energies 共lower panel兲 and absolute values of mag- atom and a fixed c/a ratio of 2.73, without relaxing the

netic moments of the Fe atoms 共upper panel兲 as a function of the atomic positions, we obtained a value which is 135 meV

volume per atom. Dotted vertical lines mark the experimental value above the corresponding energy obtained with full relax-

共Ref. 7兲 (10.06 Å3 /atom) for the volume per atom of hematite at ation. Therefore we ascribe the discrepancy to the results of

ambient conditions and are drawn to guide the eye. As zero energy Sandratskii and co-workers to the fact that we have allowed

the global energy minimum is taken, corresponding to the AF ⫹ for full relaxation of the cell shape (c/a ratio兲 and the atomic

⫹⫺⫺ state, at a volume of 10.00 Å3 /atom. The straight solid line positions inside the supercell. Sandratskii et al. present their

is tangent to the AF ⫹⫹⫺⫺ and the FM ⫹⫹⫹⫹ curves and results for a fixed geometry. This might also be the reason for

marks a structural transition at a pressure of 14 GPa. their FM magnetic moments being about as large as the AF

ones, while in our calculations the moments differ by more

The AF solutions slightly vary in magnetic moments, with than 0.8 B . The small difference in energy between FM and

all moments being ⬇3.4 B in magnitude. This is about AF states obtained by Catti et al.29 has already been

1.5 B lower than the experimental moments.53 In contrast to explained32 to be due to the complete neglect of correlation

the results of Sandratskii et al.,32 who obtain almost the same in HF theory.

moments for AF and FM ordering, the moments of the FM When we consider lower volumes we observe a collapse

solution are about 1.0 B lower in our calculation. This re- of the magnetic moments, from a high-spin 共HS兲 to a low-

flects the frustration of the magnetic exchange interactions in spin 共LS兲 state, which occurs at 8.86 Å3 for the AF ⫹⫹⫺⫺

the FM configuration. solution, and around 9.1, 9.3 and 9.2 Å3 for the

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

LSDA 32 0 3.72

HF 31 0 4.74 2.70 2.877 4.033

AF ⫹⫺⫹⫺ GGA This paper 211 3.38 2.76 2.959 3.958

LSDA 32 190 3.80

AF ⫹⫺⫺⫹ GGA This paper 224 3.45 2.69 2.803 4.000

LSDA 32 204 3.74

FM ⫹⫹⫹⫹ GGA This paper 388 2.60 2.85 2.689 4.380

LSDA 32 489 3.73

HF 31 37

NM GGA This paper 680 2.83 2.761 4.280

165107-4

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.

Expt. 共Ref. 6兲 10.06 0.1053 0.3056 2.731 2.896 3.977 178, 225 共231,a 258b兲

AF ⫹⫺⫹⫺ 共HS兲 10.13 3.42 0.1073 0.3122 2.757 2.976 3.959 134

AF ⫹⫺⫹⫺ 共LS兲 8.85 1.00 0.0979 0.3110 2.775 2.610 4.052 206

AF ⫹⫺⫺⫹ 共HS兲 10.13 3.48 0.1031 0.3047 2.690 2.812 4.010 169

AF ⫹⫺⫺⫹ 共LS兲 8.88 1.17 0.0962 0.3120 2.714 2.526 4.038 212

FM ⫹⫹⫹⫹ 8.79 0.0960 0.3131 2.795 2.564 4.111 249

NM 8.73 0.0966 0.3150 2.811 2.582 4.102 271

a

Reference 6.

b

Reference 20.

⫹⫺⫹⫺, ⫹⫺⫺⫹, 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

parameters x O and z Fe , plotted as z Fe⫹0.25 共middle兲, and Fe-Fe

distances 共lower panel兲 with pressure, together with experimental

data taken from Ref. 20.

tural parameters, whereas we do not see a transition in the

experimental values.

The c/a values from our calculation are larger than the

ones found in experiment.6,7,20 The agreement of all param-

eters and their pressure dependence with experiment is rea-

sonable for pressures below p c . Due to the transition at p c

this agreement becomes poor for pressures above 14 GPa.

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.

165107-6

FIRST-PRINCIPLES CALCULATION OF THE . . . PHYSICAL REVIEW B 69, 165107 共2004兲

and Catti et al. calculated about 11 eV within HF. The small

discrepancies between our and previous DFT calculations

can be ascribed to the use of the ASA in the LMTO and ASW

work 共whereas we use a full-potential technique兲, the dra-

matic overestimation of the gap calculated within HF is due

to the complete neglect of electronic correlations. The dis-

agreement with experiment may be traced back to some ex-

tent to the amount of mixing of Fe 3d and O 2p states,

which plays an important role in the characterization of the

insulating nature of hematite. Whereas the mixing is nearly

absent in the HF study and clearly underestimated in the

LSDA calculations, a strong mixing across the entire range

of the valence band is present in our calculations. At the

upper edge of the valence band we observe Fe states and O

states in comparable amounts. The Fe 3d DOS is even a bit

larger than the O 2p DOS, whereas it is experimentally con-

firmed that the valence-band edge in ␣ -Fe2 O3 is dominated

by oxygen 2p states, making hematite a charge-transfer in-

sulator. This deficiency in our calculations originates from

the underestimation of the on-site Coulomb interaction of the

Fe d electrons and can be compensated by introducing an

additional parameter in the density functional, as will be

shown in Sec. VI.

Figure 5 shows the partial DOS’s for the FM solution at

the equilibrium volume of the FM phase of 8.79 Å3 /atom.

We find half-metallic hematite under these conditions, the

valence-band edge being clearly dominated by Fe 3d states.

The HS-LS transition therefore turns out to be an insulator-

metal transition.

functional we obtain a quite reasonable description of the

structural properties at low pressures and the magnetic

ground state of hematite. But still several evident shortcom-

ings of the DFT remain. The magnetic moments of the Fe

atoms and the band gap are too small, and the character of

the gap contradicts the accepted charge-transfer character.

Most importantly, however, we find ␣ -Fe2 O3 to be unstable

under even modest compression against a HS-LS transition

coupled to an isostructural transition. Furthermore, the ener-

getic order of the possible magnetic phases changes upon the

transition, with the FM phase being favored at pressures be-

yond ⬃ 14 GPa. This contradicts the observed stability of

the corundum-type AF⫹⫹⫺⫺ phase up to about 50 GPa

and demonstrates the need to account for electronic correla-

tion effects.

A. Crystal structure and magnetization

As discussed before, conventional DFT gives the correct FIG. 5. Orbital projected DOS 共PDOS兲 for the FM solution of

stable antiferromagnetic ground state but underestimates the Fe2 O3 , calculated within the GGA. The left 共right兲 panel shows

band gap and magnetic moments of ␣ -Fe2 O3 . It also predicts spin-up 共spin-down兲 Fe e g , Fe t 2g , and O 2p projections. The

the valence-band edge to be Fe 3d dominated, whereas the orbitals are projected onto Wigner-Seitz spheres.

165107-7

G. ROLLMANN, A. ROHRBACH, P. ENTEL, AND J. HAFNER PHYSICAL REVIEW B 69, 165107 共2004兲

netic moment, and band gap with U for the GGA⫹U calculations.

The exchange parameter J was kept constant at 1 eV. So U

⫽1 eV corresponds to the GGA limit.

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

165107-8

FIRST-PRINCIPLES CALCULATION OF THE . . . PHYSICAL REVIEW B 69, 165107 共2004兲

show that the structural phase transition is followed by an

insulator to metal transition. Especially in the GGA⫹U case,

the band gap closes abruptly. Whereas at a volume of

⬃7.4 Å3 /atom, the band gap is ⬃1.2 eV, it drops to zero at

⬃6.9 Å3 /atom. However, as shown by Rozenberg et al.,

these transitions are preceded by a transition to a nonmag-

netic orthorhombic Rh2 O3 共II兲-type phase at about 50 GPa.

This, however, is beyond the scope of the present study.

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

共IPS兲 spectra 共Ref. 12兲 for Fe-3d states together with an estimate of

the photoemission spectra calculated from the Fe-3d and the O-2p

DOS using photoionization cross sections of Yeh and Landau 共Ref.

59兲 for different values of U. A smearing parameter of ⫽0.8 was

used to broaden the DOS.

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

properties of rhombohedral ␣ -Fe2 O3 for different volumes of

the primitive unit cell in the framework of DFT using the

GGA. It could be shown that although ground-state proper-

ties such as c/a ratio and atomic positions agree well with

experimental data, electronic properties such as band gap,

but also magnetic moments, are in substantial disagreement

with experiment. Furthermore we observe a HS-LS AF-FM

insulator-metal transition at a pressure of 14 GPa which is

not seen in experiment. Above that pressure structural pa-

rameters differ strongly from the corresponding experimental

values. This transition turns out to be due to the improper

description of the on-site Coulomb interaction in conven-

tional DFT in combination with the GGA. When introducing

a Hubbard like term in the density functional 共DFT⫹U), the

transition is shifted to lower volumes with increasing U and

eventually disappears for U⭓4 eV, resulting in strongly im-

proved values for magnetic moments, internal degrees of

freedom, and band gap as well as better agreement of the

FIG. 9. Orbital projected DOS 共PDOS兲 for the AF ⫹⫹⫺⫺ density of states with experimental PES and IPS spectra. A

solution of Fe2 O3 , calculated within the GGA⫹U with U⫽4 eV. further increase of U does not lead to better agreement, the

The left 共right兲 panel shows spin-up 共spin-down兲 Fe e g , Fe t 2g , and band gap gets too large and occupied Fe 3d states are shifted

O 2p projections. to too low energies. We consider U⫽4 to be the value for

165107-10

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.’’

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165107-12

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