Ceramics International 46 (2020) 20472–20476

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Antiferromagnetic-ferromagnetic transition in Bi-doped LaFeO3 T

nanocrystalline ceramics
Qingrong Yaoa, Chuang Tiana, Zhao Lua,b,∗, Jiang Wanga, Huaiying Zhoua, Guanghui Raoa,∗∗
a
School of Materials Science and Engineering, Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin, 541004, PR China
b
Guangxi Key Laboratory of Processing for Non-ferrous Metals and Featured Materials, Guangxi, 530004, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: A series of nanocrystalline La1-xBixFeO3 (0.0≤x ≤ 0.5) ceramic powders were successfully prepared by the sol-
Sol–gel gel method. X-ray diffraction and transmission electron microscopy were used to investigate the crystal structure
Perovskite evolution and hyperfine interactions of the samples. The average diameter of the powders was revealed to be
Crystal structure approximately 80 nm. All the samples were crystallized into an orthorhombic crystal structure (space group
Magnetic properties
Pnma) with no second phase. The magnetization of the Bi-doped samples obviously improved with increasing Bi
LaFeO3 nanoparticles
content. A remarkable antiferromagnetic/ferromagnetic transition was detected at x ≥ 0.2, and a high coercive
field of 23.05 kÖe was obtained with x = 0.5. The high correlation between the magnetization parameters and
bonding characteristics indicated that significant stretching of the Fe3+-Od2- bonds and a decrease in Fe3+-Od2--
Fe3+ linkage angles were the main origins of the strong ferromagnetism in the Bi-doped systems.

1. Introduction induce an exchange bias in FM materials.

Perovskite-type LaFeO3 oxide has recently attracted considerable
attention due to its appealing ferroelectric, catalytic, optical and mag-
netic properties. It is a candidate for use in solid oxide fuel cells, en-
vironmental catalysts, magneto-optical devices and magnetic data sto-
rage devices [1–4]. Under ambient conditions, LaFeO3 crystallizes in an
orthorhombically distorted perovskite structure with space group Pnma
[5,6]. From a magnetic point of view, LaFeO3 can be described as two
interpenetrating pseudo-cubic face-centred sublattices, which consist of
slightly canted FeO6 octahedral units [3]. The iron spins on the two sub-
lattices are nearly parallel but have opposite spin orientations from
each other, which leads to G-type antiferromagnetic (AFM) ordering
[3,7,8]. Although bulk LaFeO3 is AFM, LaFeO3 nanoparticles often ex-
hibit increasing net magnetization due to the presence of an un-
compensated surface [4,9]. In addition, the magnetic configuration of
LaFeO3 can also be altered by distortion of the interionic distances and
the bond angles with tilting of the FeO6 octahedra around their own
axes, which inhibits the AFM effect and enhances the net magnetic
moment perpendicular to the AFM axis [1,10]. This suggests that the
physical properties of LaFeO3 could be controlled by crystal structure
modulation. If large ferromagnetic (FM) property is promoted in the
LaFeO3 system, it would have potential applications in spintronics or to
Lattice site substitution with different ionic radii is an effective way
to modulate the crystal structure and hence results in uniform canted
AFM ordering. It has been observed that the partial substitution of La
atoms by elements like Na [11], Zn [12,13], Ce [1,14], Gd [2] and Al
[15] suppresses the AFM effect and enhances the FM properties of
LaFeO3. Although the material has been the subject of extensive studies,
the origin of the AFM-FM transition in ionic-doped LaFeO3 nano-
particles is still elusive, and experimental evidence supporting a direct
connection between the bonding characteristics and magnetic beha-
viour is still lacking.
The motivation for this work was to study in detail the structural
evolution and magnetic properties of Bi-doped LaFeO3 nanoparticles. A
large coercive field and remnant magnetization arising from the canted
AFM order in Bi-doped LaFeO3 nanoparticles were observed. Systematic
investigation of the bond-bond characteristics allows us to better un-
derstand the nature of the AFM-FM transition in Bi-doped LaFeO3 na-
noparticles.
2. Experimental procedures
Polycrystalline powders with the formula La1-xBixFeO3
(0≤x ≤ 0.50) were prepared using the conventional sol-gel method.

∗
Corresponding author. School of Materials Science and Engineering, Guangxi Key Laboratory of Information Materials, Guilin university of Electronic Technology,
Guilin, 541004, PR China.
∗∗
Corresponding author.
E-mail addresses: luzhao_gx@163.com (Z. Lu), rgh@guet.edu.cn (G. Rao).

https://doi.org/10.1016/j.ceramint.2020.05.146
Received 18 April 2020; Received in revised form 13 May 2020; Accepted 14 May 2020
Available online 16 May 2020
0272-8842/ © 2020 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Q. Yao, et al.
Analytical grade, La(NO3)3·6H2O, Fe(NO3)3·9H2O, and Bi(NO3) 3·5H2O
purchased from Sigma–Aldrich Chemicals Co., Ltd. were mixed stoi-
chiometrically and dissolved in 1:5 HNO3 to form an aqueous solution.
An appropriate proportion of ethylene glycol and citric acid were
added, and then the solution was stirred for a few hours at approxi-
mately 70 °C to ensure its homogeneity. The obtained mixture was
dried at 80 °C and ground to powder. The precursor powders were
calcined at 800 °C for 4 h to form nanocrystal samples. The crystal
structures of the samples were identified with powder X-ray diffraction
(PANalytical X'pert) using Cu Kα radiation (λ = 1.5406 Å). The dif-
fractometer was operated at 45 kV and 40 mA, and the 2θ scan ranged
from 10 to 140° with a step size of 0.02 and a counting time of 2 s per
step. The crystal structure parameters were refined by the Rietveld
technique using FULLPROF software [16]. Scanning electron micro-
scopy (SEM) (FEI Quanta FEG 450) and high resolution transmission
electron microscopy (HRTEM) (Talos F200X, FEI Inc., USA) were used
to examine the morphology and microstructures of the samples. Mag-
netization measurements were performed using a Quantum design
PPMS-VSM system with magnetic field cycling between −80
and + 80 kOe at 300 K.
3. Results and discussion
The X-ray powder diffraction (XRD) patterns in Fig. 1 show the
structural evolution of the La1-xBixFeO3 with various Bi contents at
room temperature. All peaks in the diffraction patterns could be in-
dexed to an orthorhombic crystal structure in the space group Pnma,
indicating that all the powder samples comprised a single phase with no
detectable secondary phases. The structural parameters of the La1-
xBixFeO3 were analysed by the standard Rietveld technique. The initial
lattice parameters and atomic positions of the unit cell were taken from
those for orthorhombic LaFeO3 with space group Pnma and lattice
parameters a = 0.5568, b = 0.7856 and c = 0.5554 nm [5]. However,
the 4c site was occupied by a mixture of La/Bi in the space group. After
the final cycle of refinement, a good match between the observed and
calculated profiles in Fig. 2a and b (only two representative patterns for
x = 0.1 and x = 0.5 are shown) and the low Rp and Rwp values sum-
marized in Table 1 further corroborate the formation of a single phase
over the whole composition range (x ≤ 0.50). The variations in the
refined lattice parameters and unit cell volume (V) of the samples as a
function of Bi concentration are displayed in Fig. 2c and d, respectively.
The lattice parameters and V slightly increase with increasing Bi con-
centration, which is also consistent with the subtle shifting of the Bragg
peaks towards lower 2θ values (see the magnified patterns in the inset
Fig. 1. X-ray diffraction patterns of La1-xBixFeO3 (0≤x ≤ 0.50). The peaks
corresponding to the (121) plane are enlarged in the upper right corner.
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Ceramics International 46 (2020) 20472–20476
of Fig. 1). The slightly larger ionic radius for Bi3+ (1.17 Å) than that for
La3+ (1.16 Å) could be responsible for the increase in the lattice
parameters. Although the lattice expansion of the unit cell is small, a
further increase in the Bi content (x > 0.50) may promote the phase
transition due to the accumulation of lattice distortion energy. Thus, we
used a cell distortion factor δ (δ = 0 for the ideal cubic perovskite) [17]
to estimate the possible critical concentration of phase transition:
δ = 10 4 × [(a/ 2 − ap)2 + (b/2 − ap)2 + (c / 2 − ap)2]/3ap2 , where
ap = (a/ 2 + b/2 + c / 2 )/3. The calculated value for the x = 0.5
compound (δ = 0.0096) is very close to zero, suggesting that a further
increase in the Bi content could lead to a cubic structure. This is con-
sistent with our previous report [18] for the crystal structure of
Bi0.6La0.4FeO3 (that crystallized into a cubic structure in space group
Pm3m with lattice parameters a = 0.3947 nm at ambient temperature)
and the work of Rusakov et al. [19].
The SEM micrographs (x = 0.1, 0.3 and 0.5) displayed in Fig. 3
indicate that all the powders have a nearly spherical shape with a
certain degree of aggregation. Their average diameter is revealed to be
approximately 80 nm. There is no obvious change in the morphology
for the sample with different Bi contents (Fig. 3). Fig. 4a shows a bright-
field TEM image of a representative specimen with x = 0.5. The par-
ticle shape and size of the powders obtained from the TEM micrograph
are consistent with those observed by SEM. The agglomerated nano-
particles contain numerous nanocrystallites. The selected area electron
diffraction (SAED) inserted in Fig. 4a shows ring patterns. Each ring in
the pattern can be indexed to a certain crystalline plane of the or-
thorhombic La0.5Bi0.5FeO3 structure according to the aforementioned
refinement of XRD pattern, indicating that the doped sample is poly-
crystalline. The HRTEM micrograph (x = 0.5) containing the grain
boundary in Fig. 4b reveals that the nanoparticles exhibit clearly re-
solved lattice fringes. The lattice fringes with interplanar spacing (d) of
0.285 nm in grain-1 can be assigned to the (121) plane of the orthor-
hombic La0.5Bi0.5FeO3 structure, and the fringes (d = 0.394 nm) in
grain-2 correspond well to the (101) plane of the orthorhombic
La0.5Bi0.5FeO3 structure, indicating the formation of a random or-
ientation and high-quality single-phase orthorhombic La1-xBixFeO3 na-
nocrystallites.
To investigate the magnetic properties of Bi-doped LaFeO3, the
magnetic hysteresis loops (M − H curves) of the La1-xBixFeO3 (x ≤ 0.5)
measured at room temperature are shown in Fig. 5a. The values of the
magnetic parameters such as the remanent magnetization (Mr) and
coercivity (Hc), are listed in Table 1. In contrast to the nearly linear
relationship of the M − H curve for bulk LaFeO3 [3], the nanocrys-
talline LaFeO3 (x = 0.0) displays distinct ferromagnetic properties with
an Mr of 0.050 emu/g and a Hc of 3.55 kÖe due to the uncompensated
spins at the surface [4,9,20]. However, the magnetic parameters are
still small, indicating that the pure LaFeO3 nanocrystallites are mainly
dominated by AFM ordering. Similar magnetic behaviour can also be
observed in the sample with x = 0.1, but the Mr and Hc values are
slightly enhanced. Interestingly, the hysteresis loops of the specimens
with x ≥ 0.2 exhibit a classical ferromagnetic shape, suggesting that
there are obvious FM interactions of the ion spins. The Hc is found to
increase from 17.47 kÖe (x = 0.2) to 22.82 kÖe (x = 0.4) and further
rise to a maximum value of 23.05 kÖe (x = 0.5). Moreover, the value of
Mr also gradually increases with increasing Bi concentration and
reaches a maximum value of 0.341 emu/g for x = 0.5. The remarkable
enhancement in the Hc and Mr values clearly indicates the occurrence of
the AFM-FM transition in the Bi-doping system.
It is worth mentioning that the introduction of Bi has a limited in-
fluence on the morphology and particle size of the La1-xBixFeO3 com-
pounds, as mentioned above. The most likely cause for the surprising
ferromagnetic properties could be the bond-bond characteristics in the
crystalline structure. Although Fig. 2c shows that all the lattice para-
meters increase with Bi substitution, the detailed changes of the lattice
parameters in unit cell are different, i.e., c almost linearly increases,
while a and b deviate from a linear relationship. The uniform increase
Q. Yao, et al. Ceramics International 46 (2020) 20472–20476

Fig. 2. Observed intensities (crosses) and calculated XRD diffraction patterns for representative La1-xBixFeO3 with x = 0.1 (a) and x = 0.50 (b). The vertical lines
indicate the peak positions. The differences between the observed and calculated intensities are shown at the bottom of the figure. (c) and (d) display the variations in
the lattice parameters and unit cell volumes for La1-xBixFeO3 (0≤x ≤ 0.50), respectively.

Table 1
Magnetization parameters, bonding characteristics and Rietveld refined structural parameters for the La1-xBixFeO3.
x Magnetic parameters Bond length (Å) Bond angles (o) Fitted goodness

3+
Mr(emu/g) Hc kÖe) Fe -Oc2- Fe 3+
-Od 2-
Fe 3+ 2-
-Od -Fe 3+
Rp (%) Rwp(%)

0.0 0.050 3.55 2.010 2.018 158.02 13.80 11.60

0.1 0.086 6.04 2.002 2.021 156.00 11.80 9.63
0.2 0.207 17.47 1.997 2.027 154.38 5.66 5.66
0.3 0.313 17.82 1.996 2.039 154.10 5.19 5.19
0.4 0.324 22.82 1.985 2.065 150.06 5.89 5.89
0.5 0.341 23.05 1.983 2.068 149.53 7.41 7.41

Fig. 3. SEM images of nanocrystalline La1-xBixFeO3 ceramic powders: (a) La0.9Bi0.1FeO3; (b) La0.7Bi0.3FeO3; and (c) La0.5Bi0.5FeO3.

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Fig. 4. TEM images of nanocrystalline La0.5Bi0.5FeO3 ceramic powders: (a) bright-field images with the corresponding SAED pattern and (b) high magnification
image of the region marked with a white box in (a).

Fig. 5. (a) Magnetization hysteresis (H–M) curves at room temperature for La1-xBixFeO3 (0≤x ≤ 0.50) nanocrystallites and (b) 3-D view of representative refined
crystal structures (x = 0.1 and x = 0.5), which shows the Fe3+-Od2--Fe3+ bond angle is significantly tilted about the [110] direction. (c) G-type spin ordering
configuration on the (001) plane of the representative La1-xBixFeO3(x = 0.1 and x = 0.5), viewed along [101] direction and (d) concentration dependence of
magnetization parameters (Mr, Hc) and bonding characteristics (Fe3+-Od2-, Fe3+-Oc2- bond length and Fe3+-Od2--Fe3+ bond angle).

in the lattice parameters in unit cell volume may suggest that there are
significant distortions of the bond length and bond angle in the crystal
structure. The quantitative structural information, like the bond length
for Fe3+-Oc2-, Fe3+-Od2- and the bond angle for Fe3+-Oc2--Fe3+ and
Fe3+-Od2--Fe3+ in the refined structures, is summarized in Table 1. As
Bi is introduced into LaFeO3, the Fe3+-Od2- bond stretches from
2.018 nm (x = 0) to 2.068 nm (x = 0.5), whereas the Fe3+-Oc2- bond
distance decreases from 2.010 nm (x = 0) to 1.983 nm (x = 0.5). The
increase in the Fe3+-Od2- bond distance could lead to a decrease in the
Fe3+-Od2--Fe3+ linkage angle (Table 1), which significantly tilts the
FeO6 octahedra about the [110] direction (the apical Fe3+-Od2- deviates
from the (010) plane and closes to (100) plane), as seen in the 3-D views
of the representative crystal structures (x = 0.1 and x = 0.5) in Fig. 5b.
On the other hand, the shrinkage of the Fe3+-Oc2- bond inevitably en-
larges the bond angle of the Fe3+-Oc2--Fe3+ (Fig. 5b) because Oc ions
occupy the (x, 1/4, z) site and Fe ions are in a special position (0, 0, 0.5)
in the space group.
Actually, in orthoferrite LaFeO3, each Fe ion has superexchange
interaction with the six nearest neighbouring Fe ions in a nearly colli-
near antiferromagnetic configuration (G-type). The spin direction of the
Fe ions has been revealed to be parallel or nearly parallel [100] di-
rection (a-axis) by powder neutron diffraction [3,7]. However, the
canting of spins at small angles due to Fe3+-O2--Fe3+ superexchange
coupling leads to a small net magnetic moment perpendicular to the a-

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axis [1,5,6]. Fig. 5c shows spin configuration of the Fe ions on the (001)
plane for the x = 0.1 and x = 0.5 systems, viewed along the [101]
direction. The decrease in the Fe3+-Od2--Fe3+ linkage angles weakens
the anti-parallel spin alignment along the a-axis but enhances the
parallel spin component along the [010] direction (b-axis). Fig. 5d
shows the variations of Fe3+-Od2--Fe3+ linkage angles and magnetic
parameters (Mr and Hc) with the Bi-substitution contents. The variation
of the Fe3+-Od2--Fe3+ bond angle with Bi content is consistent with that
of the Mr and Hc values, except for an abnormal Mr for x = 0.3. This
reveals that the decrease in the Fe3+-Od2--Fe3+ bond angle plays a
major role in tilting spin direction of Fe ions in doped systems. It is
worth mentioning that the superexchange interaction strength may also
increase as the Fe3+-O2- bond distance decreases, as discussed by Gilleo
[21,22] and Anderson [23]. It is clear in Fig. 5d that the variations in
the Hc and Mr values are strongly correlated with Fe3+-Oc2- bond
length, indicating that the spins of the Fe ions could be pinned by the
stronger Fe3+-Oc2--Fe3+ superexchange interaction upon Bi doping due
to the shorter Fe3+-Oc2- bond length. Thus, Bi-doped LaFeO3 systems
become magnetically harder.
4. Conclusions
In summary, the effects of Bi doping on the structure and magnetic
properties of nanocrystalline LaFeO3 are investigated. It is revealed that
all the doped compounds are single phase for Bi contents x ≤ 0.5. The
striking AFM/FM transition occurs at x ≥ 0.2. Large FM parameters are
obtained, and they reach maximum value at x = 0.5 (Hc = 23.05 kÖe
and Mr = 0.341 emu/g). By carefully analysing the interrelations be-
tween the magnetic parameters and bonding characteristics in the unit
cell, we revealed that the stretching of Fe3+-Od2- bonds and decrease in
Fe3+-Od2--Fe3+ linkage angles result in significant tilting of FeO6 oc-
tahedra about the [110] direction in the Bi-doping systems, which is the
main origin of the strong ferromagnetism. Therefore, by controlling the
Fe3+-Od2- bond and Fe3+-Od2--Fe3+ linkage angle distortion behaviour
based on the crystal structure, it is possible to optimize the magnetic
properties of LaFeO3 nanocrystallites in the future.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
This work was financially supported by the National Natural Science
Foundation of China of China (No. 51761007 and No. 51871066) and
Technology Base and Special Talents at Guangxi (Grant No.,
2018AD19088 and No.AD19110078). The Guangxi Natural Science
Foundation (Grant No., 2019GXNSFAA245003 and No.
2018GXNSFAA294069) the Scientific Research Foundation of Guilin
University of Electronic Technology (UF18016) and Guangxi Key
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Ceramics International 46 (2020) 20472–20476
Laboratory of Processing for Non-ferrous Metals and Featured Materials
(2019GXYSOF08), and Guangxi Key Laboratory of Information
Materials (191012-Z) are acknowledged. The authors thank the support
from the foundation for Guangxi Bagui scholars.
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