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Electronic Structure and Magnetic Properties of PbMO3
Electronic Structure and Magnetic Properties of PbMO3
Electronic Structure and Magnetic Properties of PbMO3
Aytaç Erkişi
Department of Physics Engineering, Hacettepe University,
Beytepe, Ankara 06800, Turkey
Gökhan Gökoğlu
Department of Physics, Karabük University, Karabük 78050, Turkey
ggokoglu@karabuk.edu.tr
We present the electronic, magnetic and structural properties of the magnetic transition
metal oxides PbMO3 (M = Fe, Co, Ni) in cubic perovskite structure. The calculations are
based on the density functional theory (DFT) within plane-wave pseudopotential method
and local spin density approximation (LSDA) of the exchange-correlation functional. On-
site Coulomb interaction is also included in calculations (LSDA + U ). The systems are
considered in ferromagnetic (FM) and G-type antiferromagnetic (G-AFM) order. FM
structures are energetically more favored than G-AFM and than non-magnetic states
for all the systems studied. The spin-polarized electronic band structures show that
all the structures have metallic property in FM order without Hubbard-U interaction
(Ueff = 0). However, the inclusion of on-site Coulomb interaction (Ueff = 7 eV) opens
a semiconducting gap for majority spin channel of PbFeO3 and of PbNiO3 resulting in
a half-metallic character. PbCoO3 system remains as metallic with LSDA + U scheme.
Bonding features of all structures are largely determined by the hybridizations between
O–p and d-states of transition metal atoms. The partial magnetic moment of Fe atom
in PbFeO3 is enhanced by inclusion of Hubbard-U interaction (2.55 µB ⇒ 3.78 µB ).
Total magnetic moments of half-metallic PbFeO3 and of PbNiO3 compounds are very
close to integer values.
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1. Introduction
The cubic transition metal oxide materials with perovskite structure (ABO3 ) are
very important due to their various invaluable physical properties like multiferroic-
ity, i.e., strong coupling between electric and magnetic degrees of freedom. The
perovskite compounds are a large set of combinations of elements with larger size
and 12-coordinated cation (A) and smaller size and 6-coordinated cation (B) con-
structing a BO6 octahedra at the eight corners of a cube. Some perovskites are
largely used as a substrate in growth process of oxide materials, such as high-Tc
layered superconductors and colossal magnetoresistance materials.1 SrSnO3 and
BaSnO3 are known as sensitive to humidity, so they are potential candidates for
humidity sensors.2 On the other hand, BaMnO3 and SrMnO3 have catalytic activity
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and are able to dissociate NO and NO2 gases.3–5 BaMnO3 surfaces performed well
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(LSDA) of the density functional theory (DFT). The rest of the paper is organized
as follows: The details of computational methods and numerical parameters used
in calculations are given in Sec. 2. The results of electronic structure calculations
are discussed in Sec. 3. Then paper concludes with a summary in Sec. 4.
2. Computational Details
All the calculations presented in this work have been carried out using the
PWscf code, distributed with the Quantum ESPRESSO package.14,a The exchange-
correlation potential is approximated by LSDA of the DFT.15,16 Ultrasoft pseudopo-
tentials (USPP) are used for all the atoms in composition. The electronic configu-
rations of the atoms in compositions are as follows: Pb: 6s2 6p2 5d10 , O: 2s2 2p4 , Fe:
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3s2 3p6 4s2 3d6 , Co: 4s1 3d8 , Ni: 4s2 3d8 .
Bulk structure of cubic perovskite oxide PbMO3 conforms to E21 symmetry
with Pm3̄m space group consisting of one formula unit of atoms per primitive cell.
Brillouin zone integration is performed with automatically generated 10 × 10 × 10 k-
point mesh centered at Γ-point following the convention of Monkhorst and Pack.17
Wavefunctions are expanded in plane wave basis sets up to a kinetic energy cut-
off value of 80 Ry. These values are determined by testing convergence in self-
consistent calculations. Davidson type iterative diagonalization method18 is used in
order to solve Kohn–Sham equations with 1×10−8 Ry energy convergence threshold.
In order to get a smooth electronic density of states (DOS), Methfessel–Paxton
type smearing is applied on fermionic occupation function with 0.02 Ry smearing
parameter. The structure optimization process is performed by Broyden–Fletcher–
Goldfarb–Shanno (BFGS) algorithm which optimizes the ionic coordinates without
breaking symmetry.19 The ionic minimization is carried out until the forces on
the atoms are less than 1 × 10−4 Ry/a.u. and the displacement of the atoms are
converged to less than 0.003 a.u.
LSDA functionals fail to describe strongly correlated electron systems with lo-
calized d and f orbitals. This is mostly encountered in transition metal oxides. In
such a case, the on-site Coulomb interaction with an effective Hubbard U parameter
(LSDA + U ) is included. The on-site Coulomb (U ) and exchange (J) parameters
are not separately taken into account in the approach of Dudarev et al.,20 but the
difference U −J which is physically meaningful is applied. Then the additional term
due to interactions of the strongly correlated 3d electrons of Fe, Co and Ni is in the
following form:
U −J X
E(LSDA + U ) = E(LSDA) + [Trρσ − Tr(ρσ ρσ )] . (1)
2 σ
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In the equation above, ρ is the density matrix of 3d states of Fe, Co, or Ni having
spin σ. Hereafter, we call the difference (U − J) as a single parameter Ueff .
Fig. 1. The crystal structures of cubic PbMO3 and tetragonal supercell of G-AFM crystal
structure.
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Ferromagnetic
Antiferromagnetic
80 120 120
60 90 90
∆E [mRy]
40 60 60
20 30 30
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a b c
0 0 0
500 650 800 950 500 650 800 950 500 650 800 950
3 3 3
Volume [a.u. ] Volume [a.u. ] Volume [a.u. ]
Fig. 2. The static equation of states of (a) PbFeO3 , (b) PbCoO3 , and (c) PbNiO3 compounds
in FM and G-AFM order with LSDA + U scheme.
LSDA
PbFeO3 7.164 183.1 4.10 3.30 µFe = 2.55
PbCoO3 7.060 172.0 1.77 1.78 µCo = 1.26
PbNiO3 7.038 183.5 1.42 0.14 µNi = 0.09
LSDA + U
PbFeO3 7.288 156.5 3.73 4.04 µFe = 3.78
PbCoO3 7.010 208.1 4.83 0.24 µCo = 0.43
PbNiO3 7.095 177.8 5.27 0.92 µNi = 1.05
a (a.u.) B (GPa) B′
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AFM orders are shown in Fig. 2. LSDA + U calculations show clearly that FM
structures have 29.41, 44.14 and 19.85 Ry lower energies than G-AFM structures
for PbFeO3 , PbCoO3 and PbNiO3 systems, respectively. This situation indicates
that FM ground states are energetically more favored than G-AFM structures for
all the systems studied. We present the results of structural parameters in Table 1
for both LSDA and LSDA+U calculations in FM order. The parameters of G-AFM
structure in the LSDA + U scheme are presented in Table 2. The equilibrium lattice
constants are approximately ≈ 7 a.u. with small deviations according to system. All
compounds considered can be regarded as hard materials with high bulk moduli
values. Moreover, PbFeO3 system has large pressure derivative of bulk modulus
indicating a strong sensitivity against pressure, since bulk modulus is a monotonic
increasing function of pressure in the range of structural stability.
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majority ↑ minority ↓
6
3
E-EF(eV)
0
-3
-6
-9
a
6
3
E-EF(eV)
0
-3
-6
-9
b
6
3
E-EF(eV)
0
-3
-6
-9
c
-1
R Γ X M Γ EDOS ρ(E) [eV ] R Γ X M Γ
Fig. 3. Spin-polarized LSDA electronic band structures for (a) PbFeO3 , (b) PbCoO3 and
(c) PbNiO3 compounds. Total electronic DOS are also included between the band structures.
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majority ↑ minority ↓
6
3
E-EF(eV)
0
-3
-6
-9
a
6
3
E-EF(eV)
0
-3
-6
-9
b
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6
3
E-EF(eV)
0
-3
-6
-9
c
-1
R Γ X M Γ EDOS ρ(E) [eV ] R Γ X M Γ
Fig. 4. Spin-polarized LSDA + U electronic band structures for (a) PbFeO3 , (b) PbCoO3 and
(c) PbNiO3 compounds. Total electronic DOS are also included between the band structures.
and 4, spin-polarized electronic band structures of the systems are presented along
the high symmetry directions in Brillouin zone for LSDA and LSDA + U calcu-
lations, respectively. All the PbMO3 compounds have metallic character in their
ground state due to LSDA scheme. The bands crossing Fermi level (EF ) are 3d
states of Fe, Co and Ni atoms as seen in Fig. 5 in which orbital projected den-
sity of electronic states are given for PbMO3 . p-states of oxygen also contribute to
bands around EF . The electronic states of Pb atoms are remarkable at high energy
levels and have no distinct effect on bonding properties. Spin-up and -down states
of PbNiO3 have very similar characteristics yielding very small magnetic moment.
It can be emphasized that 3d electronic states of magnetic transition metal are
responsible for the metallicity of these systems.
In Fig. 6, spin-polarized LSDA + U calculated electronic densities of states are
shown. As clearly seen, the Hubbard U interaction has remarkable effects on elec-
tronic structure. In the majority spin channels of PbFeO3 and PbNiO3 compounds,
an energy gap appears by the inclusion of Ueff . These energy gaps are 1.36 eV and
0.96 eV for PbFeO3 and PbNiO3 , respectively, both are direct band gaps at M
point. These materials become half-metallic with a semiconducting band structure
for one spin state, while the other spin state conveys a metallic conduction. As a
typical property of half-metals, the total magnetic moments of these systems are
very close to integer values; µPbFeO3 = 4.04 and µPbNiO3 = 0.92 µB , since the elec-
tronic states about EF are solely occupied by minority spins. Hubbard U interaction
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O-p
2 Fe-d
Pb-s
EDOS ρ(E) [eV ]
-1
-1
-2
a
O-p
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2 Co-d
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Pb-p
Pb-s
EDOS ρ(E) [eV ]
-1
-1
-2
b
O-p
2 Ni-d
Pb-p
EDOS ρ(E) [eV ]
Pb-s
-1
-1
-2
c
-10 -8 -6 -4 -2 0 2 4 6
E-EF(eV)
Fig. 5. Spin-polarized LSDA orbital projected electronic DOS for (a) PbFeO3 , (b) PbCoO3 and
(c) PbNiO3 compounds.
repels the electronic states to lower energies via changing Fermi energy. Especially
in the case of PbFeO3 , the energetic difference between the majority and minority
spins of Fe–3d states are widened with almost zero density of up spin states at
EF . This is the cause of large increase in Fe magnetic moment upon inclusion of
Ueff . The p-orbital of oxygen is also slightly disturbed by the inclusion of Ueff . The
bonding properties of all structures are mainly determined by the hybridizations
between d-states of transition metal atoms and O–p states. p-states of Pb atom
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O-p
2 Fe-d
Fe-p
Pb-s
EDOS ρ(E) [eV ]
-1
1 Pb-p
-1
-2
a
O-p
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2 Co-d
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Co-s
Pb-p
EDOS ρ(E) [eV ]
-1
1 Pb-s
-1
-2
b
O-p
2 Ni-d
Pb-p
EDOS ρ(E) [eV ]
Pb-s
-1
-1
-2
c
-10 -8 -6 -4 -2 0 2 4 6
E-EF(eV)
Fig. 6. Spin-polarized LSDA + U orbital projected electronic DOS for (a) PbFeO3 , (b) PbCoO3
and (c) PbNiO3 compounds.
take place at high energy levels with no distinct effect on bonding and conduction
properties.
4. Conclusion
The electronic, magnetic and structural properties of the magnetic transition metal
oxides PbMO3 (M = Fe, Co, Ni) in cubic perovskite structure have been investigated
in detail with considering different magnetic orders. On-site Coulomb interaction
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Acknowledgments
This research was supported in part by TÜBİTAK (The Scientific & Technological
Research Council of Turkey) through TR-Grid e-Infrastructure Project, part of the
calculations have been carried out at ULAKBİM Computer Center.
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