Electronic Structure and Magnetic Properties of PbMO3

August 5, 2014 10:3 WSPC/Guidelines-IJMPB S0217979214502051
International Journal of Modern Physics B

Vol. 28 (2014) 1450205 (10 pages)
c World Scientific Publishing Company
DOI: 10.1142/S0217979214502051
Electronic structure and magnetic properties of PbMO3

(M = Fe, Co, Ni) magnetic perovskites:
An ab initio study
by UNIVERSITY OF MICHIGAN on 11/05/14. For personal use only.
Int. J. Mod. Phys. B Downloaded from www.worldscientific.com
Aytaç Erkişi
Department of Physics Engineering, Hacettepe University,
Beytepe, Ankara 06800, Turkey
Erdem Kamil Yıldırım

Department of Physics, Kırıkkale University, Kırıkkale 71450, Turkey
Gökhan Gökoğlu
Department of Physics, Karabük University, Karabük 78050, Turkey
ggokoglu@karabuk.edu.tr
Received 26 March 2014

Revised 23 June 2014
Accepted 30 June 2014
Published 5 August 2014
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.
Keywords: Oxides; ab initio calculations; electronic structure.
PACS numbers: 71.15.Mb, 71.20.Be, 75.50.Cc
1450205-1
A. Erkişi, E. K. Yıldırım & G. Gökoğlu
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
and are able to dissociate NO and NO2 gases.3–5 BaMnO3 surfaces performed well
in removing NO, when it is doped by La or Mg.3,4 The elevation of NO decomposi-

tion to a large extent makes BaMnO3 a good candidate as a catalyst together with
its low cost and high thermal stability even at temperatures higher than 1200 K.3,4
The preservation of thermal stability leads to conservation of catalytic activity.
Some cubic perovskite structures feature interesting magnetic properties in fer-
romagnetic (FM) and antiferromagnetic (AFM) order. Although most cubic per-
ovskites are known to have insulating electronic structure,1 in a recent study, it
is reported that BaMnO3 structure shows half-metallic properties both in bulk
and surface geometries in view of the density functional calculations within gen-
eralized gradient approximation.6 The most studied BiFeO3 compound is also a
magnetic perovskite with ferroelectric property below ≈ 1103 K and ferromagneti-
cally ordered below 640 K with a magnetic ordering in a single phase.7–10 BiFeO3
exhibits multiferroic phenomenon at ambient temperature having potential appli-
cations in spintronics; magnetically ordered and electrically accessed memory de-
vices.9 BiCoO3 has a C-type AFM structure in its ground state having an insulating
character with 2.11 eV energy band gap.11
In view of technological applications of cubic perovskites explained above, bulk
properties of these materials should be clarified in order to elevate the efficiency. The
PbNiO3 compound synthesized at 800◦ C under 3 GPa pressure.12 This was an or-
thorhombic phase in GdFeO3 -type structure with space group Pnma. This structure
can be transformed into a LiNbO3 -type phase with an acentric space group R3c.
The ferroelectric polarization properties of PbNiO3 have also been investigated.13
These are the high temperature and high pressure phases of the related compound.
To the best of our knowledge, there is a lack of study on electronic structure and
magnetic properties of cubic magnetic PbMO3 (M = Fe, Co, Ni) structures in liter-
ature. Moreover, the effects of on-site Coulomb interaction (LSDA + U ), which is
highly desirable in investigation of strongly correlated electron systems like tran-
sition metal oxides, on the magnetic properties of these materials is discussed in
detail. Therefore, our main goal is to perform a comprehensive investigation on
electronic structure of this set of materials within local spin density approximation
1450205-2
(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:
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
a Quantum-ESPRESSO is a community project for high-quality quantum-simulation software,

based on DFT, and coordinated by Paolo Giannozzi. See http://www.quantum-espresso.org and
http://www.pwscf.org.
1450205-3
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 .
3. Results and Discussion

The stability and structural distortions of perovskite oxides are roughly
√ determined
by Goldschmidt tolerance factor that is defined by t = (rA + rO )/ 2(rB + rO ),21
where rA , rB , rO are the ionic radii of the A, B cations and oxygen anion, respec-
tively. The values with 0.9 < t < 1.0 are energetically favored in cubic phase, while
the structures with 0.75 < t < 0.9 tend to orthorhombic phase (Pnma space group)
with a tilting of BO6 octahedra yielding lower symmetry. The calculated tolerance
factors of the systems considered are 0.92, 0.95 and 0.98 for PbFeO3 , PbCoO3 and
PbNiO3 , respectively. This situation enables us to investigate such systems in cubic

E21 crystallographic structure.
Firstly, we investigate the stable crystal structure of cubic PbMO3 (M = Fe,
Co, Ni) compounds in FM order with 5-atom cell by calculating total energies at
more than 20 different volumes. The same procedure is also applied to G-type an-
tiferromagnetic (G-AFM) structure whose crystallographic order is shown in Fig. 1
together with conventional E21 structure. The primitive cell of G-AFM structure
is modeled by a 10-atom supercell, in which the magnetic moment of 3d transition
metal cation (Fe, Co or Ni) is in opposite direction to magnetic moments of six
nearest-neighbor identical atoms. Then, we use Vinet equation of states to obtain
equilibrium structural parameters and ground state energies.22,23 The asymptotic
Fig. 1. The crystal structures of cubic PbMO3 and tetragonal supercell of G-AFM crystal
structure.
1450205-4
100 150 150
Ferromagnetic
Antiferromagnetic
80 120 120
60 90 90
∆E [mRy]
40 60 60
20 30 30
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.
Table 1. The optimized structural parameters, total magnetic moments and

partial magnetic moment of the magnetic atoms in composition for LSDA and
LSDA + U (Ueff = 7 eV) calculations in FM phase.
a (a.u.) B (GPa) B′ µtot (µB ) µatom (µB )
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
Table 2. The optimized structural parameters

for LSDA + U (Ueff = 7 eV) calculations in
G-AFM phase.
a (a.u.) B (GPa) B′
PbFeO3 7.295 153.5 6.21

PbCoO3 7.023 193.4 4.63
PbNiO3 7.065 181.3 5.79
standard errors in fitting process are less then ≈ 2% as an indication of accuracy of

the calculations. Murnaghan equation of states also give similar values with ≈ 1%
differences. The static equations of states of PbMO3 compounds in FM and G-
1450205-5
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.
The inclusion of on-site Coulomb interaction redecorates the electronic structure

yielding dramatic changes in structural parameters as well as in energy band struc-
ture and density of electronic states. The Ueff parameter is chosen as 7 eV for all 3d
transition metals in compositions. The bulk moduli of the systems, except PbCoO3 ,
are decreased together with slight increase in equilibrium lattice constants. There
are also remarkable changes in total and partial magnetic moments. The magnetic
moment of Fe atoms in PbFeO3 is largely enhanced by inclusion of Hubbard U
(2.55 µB ⇒ 3.78 µB ). The details of the interactions can be visualized by consider-
ing electronic band structures and partial electronic DOS of the systems. In Figs. 3
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.
1450205-6
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. 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
1450205-7
O-p
2 Fe-d
Pb-s
EDOS ρ(E) [eV ]
-1
-1
-2
a
O-p
2 Co-d
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
1450205-8
O-p
2 Fe-d
Fe-p
Pb-s
EDOS ρ(E) [eV ]
-1
1 Pb-p
-1
-2
a
O-p
2 Co-d
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
1450205-9
has been included in calculations (LSDA+U ), which is usually vital in investigation

of highly correlated electron systems, such as transition metal oxides. The FM and
G-AFM orders have been studied. For all three compounds, FM ground states are
energetically more favorable than G-AFM and than nonmagnetic states. The spin-
polarized electronic band structures exhibit a metallic property in FM order without
inclusion of Hubbard-U interaction (Ueff = 0). But, LSDA + U calculations present
rather interesting results. The on-site Coulomb interaction (Ueff = 7 eV) opens an
electronic band gap for majority spin channel of PbFeO3 and of PbNiO3 resulting
in a half-metallic character. As a typical property of half-metallic compounds, total
magnetic moments of PbFeO3 and of PbNiO3 compounds are very close to integer
values. These materials can have possible applications in spintronics with half-
metallic conduction and large magnetoresistance.
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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Electronic Structure and Magnetic Properties of PbMO3

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August 5, 2014 10:3 WSPC/Guidelines-IJMPB S0217979214502051

International Journal of Modern Physics B

Electronic structure and magnetic properties of PbMO3

Erdem Kamil Yıldırım

Received 26 March 2014

Keywords: Oxides; ab initio calculations; electronic structure.

PACS numbers: 71.15.Mb, 71.20.Be, 75.50.Cc

A. Erkişi, E. K. Yıldırım & G. Gökoğlu

in removing NO, when it is doped by La or Mg.3,4 The elevation of NO decomposi-

Electronic structure and magnetic properties of PbMO3

a Quantum-ESPRESSO is a community project for high-quality quantum-simulation software,

A. Erkişi, E. K. Yıldırım & G. Gökoğlu

3. Results and Discussion

PbNiO3 , respectively. This situation enables us to investigate such systems in cubic

Electronic structure and magnetic properties of PbMO3

100 150 150

Table 1. The optimized structural parameters, total magnetic moments and

a (a.u.) B (GPa) B′ µtot (µB ) µatom (µB )

Table 2. The optimized structural parameters

PbFeO3 7.295 153.5 6.21

standard errors in fitting process are less then ≈ 2% as an indication of accuracy of

A. Erkişi, E. K. Yıldırım & G. Gökoğlu

The inclusion of on-site Coulomb interaction redecorates the electronic structure

Electronic structure and magnetic properties of PbMO3

A. Erkişi, E. K. Yıldırım & G. Gökoğlu

Electronic structure and magnetic properties of PbMO3

A. Erkişi, E. K. Yıldırım & G. Gökoğlu

has been included in calculations (LSDA+U ), which is usually vital in investigation

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