Superlattices and Microstructures 63 (2013) 182–196

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Superlattices and Microstructures

journal homepage: www.elsevier.com/locate/superlattices

Review

New theoretical investigation on the electronic

structure and magnetic interaction for both cubic
SrFeO3 and CaFeO3 oxides: Comparison between
GGA and GGA + U approaches
N. Hamdad ⇑, H. Rozale, A. Lakdja, A. Chahed, O. Benhelal
Condensed Matter and Sustainable Development Laboratory, Physics Department, Faculty of Sciences, University Djillali Liabès,
Sidi Bel Abbes 22 000, Algeria

a r t i c l e i n f o a b s t r a c t

Article history: Very recently, the spin effect and the magnetic interaction in the
Received 6 April 2013 solid have played an important role to show specifics properties
Received in revised form 1 July 2013 for sciences material, especially for the magnetic oxides with
Accepted 3 August 2013
AFeO3 or AMnO3 systems (Fe–O–Fe, Mn–O–Mn bonds), whereas
Available online 19 August 2013
the magnetic moment coexist and gives differences between struc-
tures and solids. For more comprehension, we investigate both
Keywords:
Magnetic intermetallic
SrFeO3 and CaFeO3 oxides to show their structural, electronic and
Magnetic properties magnetic properties also we give a special attention to the spin
Ab initio calculation effect using a comparison between two approaches GGA and
Electronic structure GGA + U based respectively on the DFT and DFT + U theories. The
Magnetic application U-Hubbard Hamiltonian added in the DFT + U basis has amelio-
rated the obtained results. The magnetic moment for different
magnetic configurations (ferromagnetic FM, A-type anti-ferromag-
netic A-AFM, and G-type anti-ferromagnetic G-AFM) for the cubic
structure is discussed. The equilibrium lattices (a, c in Å), bulk
modulus (B, in GPa), and its pressure derivatives (B0 ) are computed,
the present results agree very well with the theoretical and exper-
imental data. The GGA + U is more efficient than the GGA. Both oxi-
des SrFeO3 and CaFeO3 exhibit the G-AFM behavior.
Ó 2013 Elsevier Ltd. All rights reserved.

⇑ Corresponding author. Tel./fax: +213 (0)48 54 11 52.

E-mail address: n.hamdad@yahoo.fr (N. Hamdad).

0749-6036/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.spmi.2013.08.002
 N. Hamdad et al. / Superlattices and Microstructures 63 (2013) 182–196 183

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
2. Models and methods in the computational details . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
2.1. Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
2.2. Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
3.1. Structural properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
3.1.1. Crystal structure and structural phase stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
3.2. Electronic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
3.2.1. Band structure and density of states (DOS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
3.2.2. The magnetic moment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
3.2.3. Charge densities analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
4. Discussion and summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195

1. Introduction

The perovskites oxides with ABO3 formula have attracted a growing importance for most scientific
researchers in different technological applications, because they received a greatest interesting theo-
retical [1–6] and experimental [7–9] studies. Recently, they have shown a remarkable development in
the magneto electronics and spintronics devices [10,11], also they are investigated in high capacity
memories (HCM), dynamic random access memories, catalytic electrodes fuel cells, optoelectronics,
sensors, laser frequency doubling, waves guides, non-volatile memories, laser host crystals, high k-
capacitors, solid fuel cell, gas separation membranes, chemical reactors [12–16]. Most of them display
the electric and magnetic properties in the same time; these types of materials are well known as mul-
tiferroic oxides [17–20]. Ideal perovskites have the general formula ABX3, where the A-site cations are
typically larger than B-site cations and similar in size to the X-site anions. While the A-site anions are
surrounded by 12 anions in cubo-octahedral coordination, the B-site cations are surrounded by 6 an-
ions are coordinated by 2 B-site cations and 4 A-site cations [21]. They have been termed an inorganic
chameleon due to the large flexibility of the structure [22]. They possess highly symmetrical cubic
structures with decreasing temperatures; they display a variety of phase transition. The perovskites
oxides have unique physical properties due essentially to the d or f states which they possess (espe-
cially 4d and 5d transition metal) [23], some have d-localized bands providing catalytically actives sur-
faces, narrow d bands with emphasized electron correlations, all these effects create diverse important
properties such as dielectric, (anti)-ferroelectric, (anti)-piezoelectric, high temperature superconduc-
tivity (HTSC), semiconductivity, colossal magneto-resistance (CMR), thermoelectricity, paramagnetic,
(anti)-ferromagnetic and multiferroic [24–34]. The existence of both charge and spin in electron opens
up existing possibilities of both specific properties the ferroelectric and ferromagnetic ones within a
harness character in the same oxide. The DFT + U description has increased the theoretical progress,
because the implementation of the new corrected Hamiltonian U-Hubbard has proved efficient re-
sults. In this paper, we present a detailed study on the ground states properties and the magnetic
interaction causes by the Fe element in both SrFeO3 and CaFeO3 oxides within a comparative study,
the theoretical analyses is given by the comparison between DFT and DFT + U basis using GGA and
GGA + U approaches, where we show that GGA + U is the most accurate one. We know already, that
the DFT implementations with different approaches introduced treat the non-hybrid exchange corre-
lation functionals widely used in the condensed matter physics application, and other metal surfaces
accurately, whereas the DFT + U approach may be a useful general method for modeling first-row
transition metal ion complexes in a condensed-matter setting, this, technique predict spin state order-
ing of the Mn or Fe atoms specially with d-electrons very well. The difference between DFT and
DFT + U can also be explained by the difference between GGA and GGA + U, where we found a tradi-
tional non-hybrid is given by GGA but a corrected by the U-Hubbard Hamiltonian added GGA + U,
184 N. Hamdad et al. / Superlattices and Microstructures 63 (2013) 182–196

Fig. 1. Three magnetic configurations considered for the cubic perovskite AFeO3 oxide with (A = Sr, and Ca). (a) Ferromagnetic
(FM), (b) anti-ferromagnetic A-type (A-AFM) and (c) anti-ferromagnetic G-type (G-AFM).

where interactions are parametrized with coulomb (U) and exchange (J) terms. The magnetic moment
can perturb the local interaction between atoms, this factor plays the important role in the present
paper, different magnetic configurations (ferromagnetic, A-type anti-ferromagnetic and G-type anti-
ferromagnetic) are employed for the cubic phase for the considerable oxides (see (Fig. 1).
The equilibrium lattices agree very well with the comparative data. Both oxides exhibit the G-AFM
behavior.

2. Models and methods in the computational details

2.1. Models

Both oxides chosen in the current work crystallized in the cubic phase [35–37,40,41,43,48], SrFeO3
is known to be a typical cubic perovskite iron oxide. Saburo Nasu [37] has confirmed that SrFeO3 is
cubic with a high valence state of Fe4+, which shows metallic conductivity at 0.1 MPa until liquid-
He temperature [37–39,9]. He has reported that a neutron-diffraction study has clarified the spin
structure below the Néel temperature of 134 K, which is a screw type, indicating competition between
the ferromagnetic and antiferromagnetic interaction for Fe atoms in the Heisenberg model [37,40].
 N. Hamdad et al. / Superlattices and Microstructures 63 (2013) 182–196 185

SrFeO3 has not shown any structural transformation up to 74 GPa, while keeping an Fe4+ state; how-
ever the Néel temperature increases up to 300 K under 18 GPa, and the external high pressure may
induce ferromagnetism in SrFeO3 due to a decrease in the interatomic distance of Fe, or an increase
in the d-band width. He, also has performed 57 Fe Mössbauer measurements of SrFeO3 under high
pressure up to 74 GPa combined with an externally applied longitudinal magnetic field in order to
clarify the existence of pressure-induced ferromagnetism [37]. Also James M. Rondinelli and Nicola
A. Spaldin have mentioned that SrFeO3 is metallic and exhibits a cubic perovskite structure at all tem-
peratures, without any evidence of a Jahn–Teller effect [41,42]. The Pm-3m space group is given by
many researchers in different works, Morimoto et al. [43] studied both CaFeO3 and SrFeO3, they men-
tioned that both oxides are known as oxides systems containing Fe4+ with the simple structure. The
interaction between 3d (Fe+4) electron and 2p(O) one is so strong that a metallic band is formed in
SrFeO3. Consequently, they said that SrFeO3 retains metallic conductivity and the valence state of
Fe seems to be constant down to 4.2 K [43–45]. However, they found that Mössbauer spectroscopy be-
low 290 K reveals that the Fe4+ in CaFeO3 changes into a ‘‘charge disproportionate’’ state with two dif-
ferent electronic states; they are assigned to Fe+3 and Fe+5, respectively [43,46,47]. Thus, the structural
investigation is of great interest, especially at low temperatures realizing such a ‘‘charge dispropor-
tionate’’ state. In the Adler et al. work [48], the SrFeO3 oxide is considered as a prototype Fe(IV) oxide,
whereas it confirmed that SrFeO3 is metallic and exhibits a cubic perovskite structure at all temper-
atures, without any evidence of a Jahn–Teller effect [48,39,49], whereas they confirmed the Rondinelli
and Spladin work [41]. Both oxides adopt the cubic structure, this phase is considered as an ideal
perovskite structure designated with Pm-3m space-group whereas the A site-cations are typically lar-
ger than the B-sites cations and similar in the size to the O anions, described in last paragraph and.
Both non-spin polarized (NSP) configuration (known with non-ferromagnetic configuration (NF))
and the ferromagnetic (FM) configuration are represented by the cubic structure with Pm-3m space
group. In the present paper, we study different magnetic configurations for both oxides (FM and
NF), and also we instigated the anti-ferromagnetic configurations (A-type and G-type for the cubic
phase), whereas the A-type anti-ferromagnetic (A-AFM) is described by the P4/mmm space group
and finally, the G-type anti-ferromagnetic (G-AFM) magnetic configuration is designated by the
Fm-3m space group.
Different researchers have confirmed that rare-earth oxides are A-AFM. P. Mandal et al. [50] repre-
sented two-type of perovskites oxides materials, with the formula RMnO3 and AMnO3 respectively (R:
rare earth), and (A: Ba, Sr, Ca and Pb, y), he confirmed that all RMnO3 are A-AFM type whereas all
AMnO3 are G-AFM, this result agrees very well with our obtained result; which allows us to say that
both SrFeO3 and CaFeO3 are G-AFM as it appears in following paragraphs where a detailed explanation
is given.

2.2. Methods

The calculation is performed using the Wien2K package [51], whereas a hybrid full potential linear
augmented plane wave besides local orbitals (L/APW + lo) [52] method within the density functional
theory DFT [53,54] based on the DFT + U description is implemented. This new description consists to
add an important factor which is the U-Hubbard Hamiltonian. From the literature, it is well known
that the theoretical calculation based on the density functional theory DFT used new approximations
in order to understand the complex system of the problems found but using a smaller basis set size.
Due to the smaller basis set and faster matrix setup, APW + lo offers a shorter run-time, in other hand
it uses less memory than LAPW, so their effects are great for calculations with a large ratio of basis
functions of atoms e.g. for open crystals structures, surfaces and molecules on surfaces [55]. Very re-
cently, we introduced the new element (U-Hubbard term) in both LSDA + U, and GGA + U [56,57],
which gives more better results than the LSDA [58] or GGA [59], this factor will be essential to treat
especially the transition metal oxides systems which posses the d and f states whereas, the corrected
exchange potential correlation is introduced using these both newly approaches LSDA + U, and
GGA + U. In the present work, we choose to perform a detailed calculation using comparison between
approximations: GGA and GGA + U in order to compute the equilibrium lattices, the obtained results
in the structural step and the calculated magnetic moment show that the GGA + U is more better than
186 N. Hamdad et al. / Superlattices and Microstructures 63 (2013) 182–196

GGA approach, for this raison we continue the calculation using only this new approach. We noted
that an exchange correlation potential based on Slater’s principle [60] is introduced on the self-
consistent calculation in these approaches, it treat the muffin-tin spheres. In this case, the space is
divided into two regions, near atoms all quantities of interest are expanded in spherical harmonic,
whereas in the interstitial region plane waves are expanded, the corrected exchange and correlation
potential implemented here needs the introduction of the U-Hubbard Hamiltonian, we take 0.49 eV
as a value of U-Hubbard term. The choice of sphere radius Rmt facilities the convergence of this
expansion. The Rmt is equal to 2.4, 1.8 and 1.5 bohr for the (Strontium and Calcium), iron and Oxygen
respectively. The wave has an expansion with RmtKmax equal to 7. The APW + lo method expands the
khon-Sham [61] orbitals inside the atomic muffin-tin (MT) spheres and plane waves in the interstitial
region. The full-relativistic approximation without spin–orbit effects was employed in the calculation
of the valence states, whereas the core levels were treated fully relativistically. The basis set inside
each MT sphere is split into core and valence subsets, whereas the core states are treated within
the spherical part of the potential only and are assumed to have especially symmetric charge density,
totally confined inside the MT spheres. To ensure high accuracy, the k-point densities and plane wave
cutoff energy are increased until convergence. The dependence of the total energy on the number of
k-points in the irreducible wedge of the first Brillouin zone (BZ) has been explored within the
linearized tetrahedron scheme by performing the calculation for 84 k-points of 14  14  14 meshes,
equivalent to 3000 k-points in the entire Brillouin zone (BZ). In all these calculations represented in
the present work, the self-consistent calculation are considered to be converged only when the
calculated total energy of the crystal is converged to less than 1mRyd. The total density of states
(DOS) was obtained using a modified tetrahedron method of Bloch et al. [62].

3. Results and discussion

3.1. Structural properties

3.1.1. Crystal structure and structural phase stability

The ideal cubic crystal structure is well designated with Pm-3m space group whereas the atomic
positions are A (0, 0, 0); Fe:1b (1/2, ½, ½), and O: 3d (0, 0, ½), both non-ferromagnetic (non-spin polar-
ized (NSP)) and ferromagnetic (FM) configurations are designated with the Pm-3m space group. The
figure shows clearly that the A site-cations are typically larger than the B-sites cations and similar
in the size to the O anions. The calculated total energy (eV) as a function of volume (bohr3) within dif-
ferent magnetic configuration (FM), (A-AFM) and (G-AFM) respectively for SrFeO3 and CaFeO3 oxides
are illustrated in (Fig. 2) computed and fitted using Murnaghan equation’s [63]. Rare-earth manganites
with the overall formula RMnO3 (R = Y, Ho, Er, Tm, Yb, and Lu) [64–66] are ferro-electromagnetic com-
pounds possessing both magnetic and ferroelectric ordering, they are multiferroic, these compounds
have anti-ferromagnetic properties with TN < 80 k. The structural properties computed in the present
work show that the G-AFM character is given by both oxides SrFeO3 and CaFeO3, which agree very well
with the P. Mandel et al. [51] report, when they examined different type of cubic perovskite oxides,
Mandal studied two-type of perovskites oxides materials, which have the formula RMnO3 and AMnO3
with (R: rare earth), and (A: Ba, Sr, Ca and Pb, y), he confirmed that all RMnO3 are A-AFM type whereas
all AMnO3 are G-AFM. The lattices parameters found in the current work agree very well with the the-
oretical data, where we found that SrFeO3 has a = 3.84 Å [36,67], 3.86 Å [41], and 0.385 nm [37] see
(Table 1).

3.2. Electronic properties

3.2.1. Band structure and density of states (DOS)

The equilibrium lattices parameters found in the last step of calculation are injected in order to
compute the electronic properties and to give a detailed study on the electronic structure for the con-
siderable oxides SrFeO3 and CaFeO3. The total and partial densities of states and the band structure
plots for the non-spin polarized configurations are given in (Fig. 3) for both oxides using the GGA
 N. Hamdad et al. / Superlattices and Microstructures 63 (2013) 182–196 187

Fig. 2. The calculated total energy (eV) as a function of volume (bohr3) within both magnetic configuration (A-AFM) and (G-
AFM) respectively for SrFeO3 and CaFeO3 oxides.

Table 1
The calculated lattices parameters (SrFeO3 and CaFeO3).

Lattice parameters Oxides

Configurations SrFeO3 CaFeO3
NSP GGA GGA + U GGA GGA + U
a (Å) 3.736 – 3.675 –
B (GPa) 204 – 219 –
B0 5.3 – 4.6 –
FM
a (Å) 3.852 3.904 3.810 3.782
B (GPa) 196 166 124 167
B0 4.6 3.7 3.9 5.5
A-AFM
a (Å) 3.242 3.853 3.702 3.795
c (Å) 3.189 3.455 3.419 3.531
B (GPa) 166 135 122 157
B0 3.7 4.4 3.2 4.7
G-AFM
a (Å) 3.800 3.829 3.756 3.766
B (GPa) 156 169 234 195
B0 3.4 3.1 4.9 4.5
Theoretical works
a (Å) 3.86a
3.84b
3.85c
3.868d
a
Ref. [36,67].
b
Ref. [41].
c
Ref. [4].
d
Ref. [5].
188 N. Hamdad et al. / Superlattices and Microstructures 63 (2013) 182–196

Fig. 3. The calculated GGA total and partial densities of states and band structures for both SrFeO3 and CaFeO3 respectively
within the GGA calculation.

approximation. Figs. 4 and 5) show the ferromagnetic (FM) and the G-AFM configurations for the
SrFeO3 and CaFeO3 oxides with spins Up and spins Dn respectively. Similar results are found for the
two oxides studied in the present work, the metallic behavior is a common factor for the two oxides.
From the non-spin polarized band structure, it is clear that both oxides exhibit the metallic behavior.
 N. Hamdad et al. / Superlattices and Microstructures 63 (2013) 182–196 189

Fig. 4. The calculated GGA + U total and partial densities of states and band structures in the Ferromagnetic (FM) configuration
with both spins (Up and Dn) for SrFeO3 and CaFeO3 oxides respectively.
190 N. Hamdad et al. / Superlattices and Microstructures 63 (2013) 182–196

Fig. 5. The calculated GGA + U total and partial densities of states and band structures in the G-type Anti-ferromagnetic
(G-AFM) with both spins (Up andDn) for SrFeO3 and CaFeO3 oxides respectively.
 N. Hamdad et al. / Superlattices and Microstructures 63 (2013) 182–196 191

Both (FM) and (NF) configurations reveal the metallic character for both oxides, but the G-AFM figures
reveal gap energy. The electronic structure for the cubic phase for the considerable oxides is investi-
gated especially within the DFT + U basis, whereas the GGA + U are given, and the U-Hubbard Hamil-
tonian is taken in consideration. The total and partial densities of states for A-AFM configuration are
illustrated in (Fig. 6). All the configurations studied in the present work, are calculated using the
GGA + U, exception the NSP configuration is given with the GGA approach. Most figures show that
these states (majorities "and minorities;) are dominated by the d-Fe states, because the Fe atom plays
an important role in the magnetic interaction for both oxides studied here. This contribution appears
clearly in the anti-ferromagnetic configurations plots, where we found two Fe atoms (Fe1 and Fe2). The
non-spin polarized configuration densities of states shows that Fe states is bigger than others atoms.
The ferromagnetic configuration plots show that Fe-states contribute more than the oxygen element,
whereas the d-Sr and p-Ca states contribution is smaller than the Fe atoms in both oxides studied. A
strong hybridization is found between the d-Sr and s-O states for SrFeO3 oxide and between the p-Ca
and s-O states for the CaFeO3 oxide. The A-AFM configuration for both oxides shows that the Fe-states
contribution is bigger than others elements, this contribution is located in the region of 15 eV to
2.5 eV (spin majorities) and in the region of 5–15 eV for the SrFeO3 oxide. For the CaFeO3 oxide,
two pikes are found (majority states at the region of 25 eV, and in minority states at 23 eV. The
O1, O2, and O3 atoms react with the same manner; their contribution is very small in spin Up and spin
Dn, whereas we found that the d-Sr and p-Ca are negligible. The G-AFM configuration for both oxides
shows also, that the Fe-states contribution is bigger than Sr, Ca, and O elements, the G-AFM plots re-
veal a small contribution for the d-Sr states (similar for the majorities "and minorities;), but the p-Ca
contribution is absent. The negligible contribution for the oxygen atom, which is found in the partial
densities figures shows a higher contribution for the spin Dn for the SrFeO3 than spin Up, and similar
for the CaFeO3 oxide. The densities plots are dominated by the d-states, this contribution appear
clearly in most figures illustrated here, the difference is given in Fe atoms states plot, where we can
see clearly that the Fe1 contribution is bigger than the Fe2 states. A wide pick is found in the
15 eV for the spin Up (SrFeO3 and CaFeO3 oxides), another is found in the region of 6 eV for the SrFe-
O3 and in the region of 3 eV for the CaFeO3 oxide respectively for the spin Dn states. Similar remark are
also found in this step of calculation, the GGA + U show very well the states, it illustrates clearly the
difference given by the (majorities "and minorities;) states.

3.2.2. The magnetic moment

The magnetic interaction plays an important role in the current study, for this raison a detailed
analysis is given for the magnetic properties. Especially, the magnetic moment is a principal factor
which can allows more comprehension on the AFeO3 oxides behaviors. In the current paper different
magnetic configurations are investigated for the cubic phase (FM, A-AFM, and G-AFM), the magnetic
moment is calculated for all these magnetic configurations and illustrated in (Tables 2–4) respectively.
The calculation of the magnetic moment is developed within a comparative context (DFT and DFT + U)
basis in a first hand, whereas differences are obtained between the two approaches employed here
(GGA, and GGA + U), in other hand also a detailed comparison is given between the two oxides SrFe-
O3, and CaFeO3 oxides studied here. The tables show the magnetic moment for the A element where
(A = Sr, and Ca), the magnetic moment for the Fe element, the magnetic moment for the oxygen ele-
ment, the magnetic moment for the interstitial region, and the magnetic total/ cell as it appear clearly.
From the values given in these tables, we remark that the GGA + U gives more higher values than
others methods, this remark is revealed from all the magnetic configurations studied in the present
work. The calculated magnetic moment in the interstitial region is equal zero in both anti-ferromag-
netic configurations (A-AFM, and G-AFM) for the two oxides, and equal 0.2 lB in the ferromagnetic
configurations (FM) for the SrFeO3 and CaFeO3 oxides using (GGA, LSDA + U, and GGA + U) methods.
From the tables, we see clearly that the magnetic moment for the oxygen and A (Sr, and Ca) atoms
is very small. The magnetic moment calculated for the ferromagnetic configuration shown in (Table 2)
is equal to 3.2 and 3.8 lB for the SrFeO3 and equal to 3.1, and 3.9 lB for the CaFeO3 oxides respectively
using GGA, and GGA + U. From the anti-ferromagnetic configurations (A-AFM) and (G-AFM) illustrated
in (Table 3) and (Table 4) respectively, two values are given for the Fe atom (Fe1 atom and Fe2 atom),
they are equal but with opposite sign. From (Table 3), same values are noted 3.0 lB and 4.0 lB for the
192 N. Hamdad et al. / Superlattices and Microstructures 63 (2013) 182–196

Fig. 6. The calculated GGA + U total and partial density of states of the A-type anti-ferromagnetic (A-AFM) configuration for
both considered oxides.

SrFeO3 and CaFeO3 oxides using respectively (GGA and GGA + U). From (Table 4), a small difference is
noted between the SrFeO3 and CaFeO3 oxides values. The GGA + U give also for the G-AFM
configurations the higher values than GGA approach. The values are equal to 2.83 and 4.11 lB for
the SrFeO3oxide, and equal to 2.81 and 4.17 lB for the CaFeO3 oxide. These values allow us much
 N. Hamdad et al. / Superlattices and Microstructures 63 (2013) 182–196 193

Table 2
Calculated magnetic moment lFe (Bohr Magneton) for the ferromagnetic (FM) configuration calculated for SrFeO3 and CaFeO3
oxides respectively using different approaches.

Materials Approaches lInterstitiel lTotal/cell (lB) lA lFe lO

SrFeO3 GGA 0.2 3.6 0 3.2 0.01
GGA + U 0.2 4.1 0 3.8 0.04
CaFeO3 GGA 0.2 3.7 0 3.1 0.1
GGA + U 0.2 4.2 0 3.9 0.01
Theoretical and experimental works
SrFeO3 Theo. 2.964a 0.152a
Exp. 3:1d
a
Ref. [36].
d
Ref. [1].

Table 3
Calculated magnetic moment lFe (Bohr Magneton) the A-type anti-ferromagnetic (A-AFM) configuration calculated for SrFeO3 and
CaFeO3 oxides respectively using both different approaches.

Materials Approaches lInterstitiel lTotal/cell (lB) lA lFe1 lFe2 lO1 lO2 lO3
SrFeO3 GGA 0 0 0 3.0 3.0 0 0.1 0.1
GGA + U 0 0 0 4.0 4.0 0 0.1 0.1
CaFeO3 GGA 0 0 0 3.0 3.0 0 0.1 0.1
GGA + U 0 0 0 4.0 4.0 0 0.1 0.1
Theoretical data
SrFeO3 3.005a 0.138a
a
Ref. [36].

Table 4
Calculated magnetic moment lFe (Bohr Magneton) for the G-type anti-ferromagnetic (G-AFM) configuration calculated for SrFeO3
and CaFeO3 oxides respectively using different approaches.

Materials Approaches lInterstitiel lTotal/cell (lB) lA lFe1 lFe2 lO1

SrFeO3 GGA 0 0 0 2.83 2.83 0
GGA + U 0 0 0 4.11 4.11 0
CaFeO3 GGA 0 0 0 2.81 2.81 0
GGA + U 0 0 0 4.17 4.17 0
Theoretical data
SrFeO3 2.970a
a
Ref. [36].

information on the magnetic interactions in both oxides investigated in this paper, and their
behaviors. First, these values show that magnetic interaction in the CaFeO3 oxide is bigger than the
SrFeO3 oxide, second remark revealed that the U-Hubbard Hamiltonian has changed extensively the
values, because a wide difference is given (DFT–GGA and DFT + U–GGA + U) where the values are equal
to 2.83, and 4.11 lB for the SrFeO3 oxide, also for the CaFeO3 oxide the values are respectively 2.81, and
4.17 lB.
The corrected Hamiltonian exchange and correlation potential introduced by the U-Hubbard term
has extensively ameliorated the obtained results, this factor shows high magnetic interactions in the
considerable oxides. The GGA + U treats with efficiency the magnetic properties more than others ap-
proach. From the current step of calculation, it appears clearly that the G-AFM configuration is more
important than others investigated for the cubic phase for both SrFeO3 and CaFeO3 oxides, which agree
very well with the conclusion given in the structural properties calculation (Both oxides exhibit the
194 N. Hamdad et al. / Superlattices and Microstructures 63 (2013) 182–196

(b) Ferromagnetic (FM) for spin Up and spin Dn.

Sr

Up
SrFeO3

Fe
O

Sr

Dn
SrFeO3
Fe

Ca

Up

CaFeO3
Fe

Ca

Dn

CaFeO3
Fe

Fig. 7. Contour plot of the total valence charge density calculated by GGA + U for the two oxides studies SrFeO3 and CaFeO3.

G-AFM configuration). Here, also the present results agree very well with the theoretical works made
by Matar, where he found that the magnetic moment carried by Fe is 3.1 lB [68].
 N. Hamdad et al. / Superlattices and Microstructures 63 (2013) 182–196 195

3.2.3. Charge densities analysis

To visualize the nature of the band character and to show the charge transfer for considerable
SrFeO3 and CaFeO3 oxides, we show the two plotted figures respectively for the ferromagnetic
configuration (SrFeO3 and CaFeO3oxides using Spin majorities Up, and the Spin minorities Dn) in
the plane (1 1 0) respectively (see Fig. 7) by DFT + U–GGA + U method. The charge densities figures
indicate that the two oxides have three types of nature chemical bonding. The interaction between
de Fe–Fe atoms (which is very higher) produces a strong covalent bonding. The ionic character is
located between the oxygen elements (O–O), whereas the Fe–Sr and Fe–Ca bonding has a weak degree
of covalency. The Fe–O is typically covalent with a weak degree of iconicity. The ionic bonding is due
essentially to the p-oxygen states. The difference is obtained by the FM plots for both oxides studied
here, where the Fe atoms contribution (Spin majorities Up) is more higher than (Spin minorities Dn),
this remark is revealed by the FM-SrFeO3 and FM-CaFeO3 plots. Also, the Sr interaction appears stron-
ger than Ca interaction. These differences are due essentially to the hybridization between the d-Sr
and p-O states, which are very higher, whereas the p-Ca has a small contribution. In order to explain
clearly the SrFeO3 and CaFeO3 interaction, we have negligee the GGA (U  J = 0) method and use only
the GGA + U (U  J = 0.49), which allows more detailed information’s on the nature bonding, also it
show clearly the transfer charge than GGA. The U-Hubbard Hamiltonian investigated in the present
calculation by the corrected exchange and correlation potential given by the GGA + U approach has
extensively ameliorated the current results, whereas the difference appears clearly. In general, both
charge densities plots (SrFeO3, and CaFeO3 oxides) are dominated by the covalent bonding, which
are due to the d-Fe states, this effect explain the level of magnetism interaction produced by the Fe
atoms, also given by the d-Sr and p-Ca states, this level is bigger in the CaFeO3 in comparison to
the SrFeO3oxide as we reported in the last paragraph (magnetic moment), we can see clearly from
both figures, where we found the Fe interaction (CaFeO3) is more higher in Fe interaction (SrFeO3)
in both spins (Up and Dn). The phenomena is explained in details in the last paragraph (Magnetic
Moment), where the magnetic total/cell for SrFeO3 is given equal to 4.1 Bohr Magneton, and magnetic
total/cell for CaFeO3 oxide is equal to 4.2 Bohr Magneton.

4. Discussion and summary

To evaluate the study given on the DFT–GGA and DFT + U–GGA + U on the band profiles and mag-
netic properties for both SrFeO3 and CaFeO3 oxides, a first-principles calculation is investigated in the
current paper, using the FP-LAPW method implemented in the Wien2K code. Different magnetic con-
figurations are studied for the cubic phase for both materials. The equilibrium lattice parameters are in
a good agreement with available theoretical and experimental data. Both oxides exhibit the G-AFM
behavior. The magnetic moment for the considerable magnetic configurations (FM, A-AFM, and G-
AFM) are calculated with different approaches (GGA and GGA + U), where the GGA + U has given
the highest values. The band structures figures show that the metallic behavior is a common factor
for the NF and FM figures illustrated in the present paper, whereas G-AFM reveal gap energy. The total
and partial densities of states plotted show that most figures are dominated by the d-Fe states which
are very higher than others elements.
The charge densities plots for the FM configuration (spins majorities Up and spins minorities Dn)
are given respectively within GGA and GGA + U approaches show that three types of nature bonding
coexist in both SrFeO3 and CaFeO3 oxides (Covalent Fe–Fe, Ionic (O–O), and Covalent with a weak de-
gree of iconicity (Fe–O, Sr–O, and Ca–O).

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