ELSEVIER Phys~a B 237-238 (1997) 11-13

Electronic band structure and lattice distortion in perovskite

transition-metal oxides
N o r i a k i H a m a d a a, *, H i d e a k i S a w a d a b, I g o r S o l o v y e v b, K i y o y u k i T e r a k u r a c

aDepartment of Physics, Faculty of Science and Technology, Science University of Tokyo,

2641 YamazakL Noda-shi, Chiba-ken 278, Japan
bjRCAT-ATP 1-1-4 Higashi, Tsukuba-shL lbaraki-ken 305, Japan
¢JRCAT-NAIR 1-1-4 HigashL Tsukuba-shi, lbaraki-ken 305, Japan

Abstract
The electronic structures of LaMO3 (M = Ti, V,..., Cu) are reviewed with particular attention to the effect of the lattice
distortion. The FLAPW and LMTO methods are employed in the band structure calculations in the LSDA, GGA and LDA+U
schemes. The experimental lattice parameters are used in these calculations. The change of the bond angle of M~)-M
gives rise to the change of the width of the d band. For LaVO3 and LaMnO3 with cooperative Jab.n-Teller distortions, the
LDA and/or GGA calculations produce orbital orders, which determine the types of spin orders. The LaTiO3 system has no
Jahn-Teller distortion, where the spin-orbit coupling might play an important role.
Keywords: Band structure calculation; Lattice distortion; Orbital order; Perovskites

1. Introduction experimental ones. For LaMnO3, the precise magnetic

Perovskite transition-metal oxides receive much at-
tention due to their rich properties resulting from the
couplings of spin, charge and lattice. We examine the
electronic structures of LaMO3 (M = Ti, V . . . . . Cu)
on the basis of the first-principles band structure cal-
culations, paying attention to the roles of the lattice
distortion.
The local spin density approximation (LSDA) fairly
well describes electronic structures ofperovskites with
M = Cr, Mn, Fe, Co, Ni and Cu for the ground-states
and single-electron excited-state properties [ 1,2]. The
ground-state magnetic structures are well reproduced
by the total energy calculations. Calculated X-ray
photoemission spectra are in good agreement with
* Corresponding author.
structure is obtained by the inclusion of the spin-orbit
interaction [3, 4]. For LaCoO3, a small energy differ-
ence between the ferromagnetic and the nonmagnetic
states is correctly reproduced, corresponding to the
energy difference between the intermediate-spin and
the low-spin states [5]. However, LSDA fails to re-
produce the insulating behavior for early transition-
metal perovskites, LaTiO3 and LaVO3. No magnetic
solution is found in LaTiO3. The generalized gradient
approximation (GGA) enhances the tendency towards
orbital polarization in LaVO3 and YTiO3, making it to
be almost insulating [6, 7]. A new LDA+U method
(LDA+U2 method), in which only de (t2g) orbitals are
treated as being localized, describes well the single-
electron properties including the band-gap nature [8].
The effective U parameter takes small values and is
larger for the early transition-metal elements than for
the late ones in these perovskite systems.

0921-4526/97/$17.00 © 1997 Elsevier Science B.V. All rights reserved

PH S 0 9 2 1 - 4 5 2 6 ( 9 7 ) 0 0 0 1 6-1
12 N. Hamada et al./ Physica B 237-238 (1997) 11-13

In this paper, we elucidate the roles of the lattice

distortion and the orbital order in the electronic struc-
ture of perovskites. All the crystal structures used in
this paper are those obtained by experiments.

2. Tilt of MO6 octahedra

F-type A-type C-type G-type
Fig. 1. Types of cooperative Jahn-Teller distortions, orbital orders
For LaMO3 (M = Ti, V , . . . , C u ) , the relative size or spin orders. Two objects, filled and open spheres, are arranged
of La 3+ to the MO6 octahedron (the tolerance factor) on the B-site sublattice in the perovskite structure. Large spheres
is too small to make a cubic structure. The MO6 oc- at the comers are B-site atoms, middle-size spheres on the edges
are oxygen atoms, and a small sphere at the body center is an
tahedron tilts to make some of the distances of La-O
A-site atom. If the same objects (e.g., filled spheres) are arranged
shorter. The M - O bond lengths and the M--O-M bond in all the B sites, the arrangement is of the F type. If the same
angles are shown in Table 1. The larger the bond objects are arranged in the a - b plane and the different objects are
length, the smaller the bond angle, i.e., the stronger arranged alternatively along the c-axis, it is the A type. If the
the tilt of the octahedron. The table shows another same objects are arranged along the c-axis and the adjacent chains
are different, it is the C type. If two different objects are arranged
interesting fact that the occupation of the dy orbital
alternatively in all the three directions, it is the G type.
makes the M - O bond length larger, as is seen on
going from Cr to Mn. The LDA band structure calcu-
lation for Lal_xBaxMnO3 in the ferromagnetic state
several types of cooperative Jahn-Teller distortions,
gives typical de bandwidths of 4.0 eV for the cubic
orbital orders or spin orders. Some of the types are
structure (/_MnOMn = 180°), 3.5 eV for the rhombo-
shown in Fig. 1.
hedral structure (/__MnOMn = 164°), and 3.0 eV for
a hypothetical orthorhombic structure without the In LaMnO3, there are two Mn-O distances in the
Jahn-TeUer distortion ( / M n O M n = 157°). a-b plane: one is 0.29 A longer than the other, as
For LaCoO3, LaNiO3 and LaCuO3, the M ~ ) - M shown in Table 2. These long bonds are ordered in
the C type. The Jahn-Teller distortion splits the dou-
angle is large, making the system nonmagnetic.
bly degenerate dy (eg) orbitals into the 3x 2 - r 2 and
)2 - z 2 orbitals, or into the 3)2 - r 2 and z 2 - x 2 or-
3. Orbital ordering in the cooperative Jahn-Teller bitals. The 3x 2 - r 2 orbital and the 3) 2 - r 2 orbital are
system ordered in the C type in accordance with the distor-
tion. If we consider the mixing of the occupied and the
We shall categorize LaTiO3, LaVO3 and LaMnO3 unoccupied orbitals, we can determine the stable spin
as the cooperative Jahn-Teller systeml There are order from the energy gain due to the hybridization.
A similar argument works well for LaVO3, where the
Table 1 GGA calculation is needed to obtain the orbital or-
Crystal Structure, mean M - O bond length, mean M - O - M bond der [6]. The LDA and GGA total energy calculations
angle and d electron configuration for LaMO3. M, O, R and T stand
shown in Table 3 partially confirm this deduction. If
for monoelinic, orthorhombic, rhombohedral and tetragonal struc-
tures, respectively we assume a hypothetical crysta! structure without the
Jahn-Teller distortion for LaMnO3, the F-type spin
Structure M-O(A) /_ MOM d electrons order becomes slightly stabler than the A-type spin
order [9].
LaTiO3 O 2.02 157 ° d~ 1
LaVO3 M 2.00 157 ° de 2
The situation is different for LaTiO3, in which the
LaCrO~ O 1.97 159 ° de 3 Jahn-Teller distortion has not been observed experi-
LaMnO3 O 2.02 155 ° de 3 dy ~ mentally. The GGA calculation with the G-type spin
LaFeO3 O 2.01 157 ° de 3 d ~ order produces no clear orbital order and no energy
LaCoO3 R 1.93 164 ° de 6
band gap. The obtained magnetic moment at the Ti
LaNiO3 R 1.93 165 ° de6 dy 1
LaCuO3 T 1.94 180 ° de 6 dy 2
site is slightly larger than the experimental value. The
spin-orbit interaction, which is not included in our
 N. Hamada et al. / Physica B 237-238 (1997) 11-13 13

Table 2 the cooperative Jahn-Teller distortion is large, which

M--O bond length, type of orbital order and type of spin order for determines the orbital order. The LSDA works fairly
the Jahn-Teller system
well in this system. For LaVO3, the distortion is small,
M-O bond lengths (A) Orbital order Spin order and the GGA calculation is needed to produce the
orbital order. The cooperative Jahn-Teller distortion
LaTiO3 2.02, 2.02, 2.02 -- G does not occur in LaTiO3, while it occurs in YTiO3.
LaVO3 2.04, 1.98, 1.98 G C Anyway, the Jahn-Teller distortion is small and com-
LaMnO3 2.19, 1.90, 1.96 C A
petes with other interactions in the Ti systems.

Table 3 Acknowledgements
Total energies (per formula-unit) of various magnetic configura-
tions measured from the most stable configuration
The present work was supported partially by New
LaVO3 LaMnO3 Energy and Industrial Technology Development
Organization (NEDO) and by the Grant-in-Aid for
Ferro. 35 meV 18 meV Scientific Research of the Ministry of Education,
A-type AF 44 meV 0
C-type AF 0 52 meV
Science and Culture of Japan.
G-type AF 52 meV 42 meV

Approx. GGA LDA References

[1] N. Hamada, H. Sawada and K. Terakura, in: Spectroscopy of

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the Jahn-Teller distortion is very subtle in these Ti
systems.
For LaCrO3 (LaFeO3), the de (and the dy) orbitals
of one spin direction are fully occupied, leading to the
G-type spin order.
4. Concluding remarks
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Y. Tokura (Springer, Berlin, 1995) p. 95.
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