Journal of Physics and Chemistry of Solids 65 (2004) 16631667

www.elsevier.com/locate/jpcs

Defect clusters in titanium-substituted spinel-related lithium ferrite

H.M. Widatallaha,b, E.A. Mooreb,*
b

a
Department of Physics, University of Khartoum, P.O. Box 321, Khartoum 1115, Sudan
Department of Chemistry, The Open University, Walton Hall, Milton Keynes, MK7 6AA, UK

Received 19 January 2004; revised 12 April 2004; accepted 12 April 2004

Abstract
The cation distribution in spinel-related titanium-substituted lithium ferrite, Li0.50.5xFe2.521.5xTixO4 has been explored using interatomic
potential and ab initio calculations. The results suggest that the cation distribution with Ti4 substituting for Fe3 on octahedral B sites and
excess Li substituting for Fe3 on tetrahedral A sites is stabilised by the formation of clusters of two octahedrally coordinated Ti4 ions and
one tetrahedrally coordinated Li ion linked through a common oxygen.
q 2004 Elsevier Ltd. All rights reserved.
Keywords: A. Ceramics; A. Magnetic materials; C. Ab initio calculations; D. Defects

1. Introduction
The lithium ferrite Li0.5Fe2.5O4 has attractive electric and
magnetic properties for microwave and memory-core
applications [1 4]. These properties can be modified by
the substitution of Fe3 on either the tetrahedral A or
octahedral B sub-lattices thus allowing the material to be
tailored for specific applications [1,5].
At low temperatures, lithium ferrite adopts an inverse
spinel structure in which all the Li ions and 3/5 of the Fe3
ions occupy octahedral B sites whilst the remaining Fe3
ions occupy tetrahedral A sites and the space group is P4332
[6,7]. At temperatures above 735 755 8C, the site
occupancy becomes disordered and the solid can be indexed
according to the space group Fd3m. For slowly cooled
samples of Ti-doped lithium ferrite with low concentrations
of Ti, it is widely accepted [8 10] that Ti4 ions replace
some of the Fe3 ions on the octahedral B sites, although
similarity in the scattering factors for Ti and Fe mean that
XRD cannot unequivocally determine the cation
distribution [10]. These samples can be considered as
solid solutions in the Li2O TiO2 Fe2O3 system and
generally contain excess Li ions above the number in
* Corresponding author. Tel.: 44-1908-655028; fax: 44-1908858327.
E-mail address: e.a.moore@open.ac.uk (E.A. Moore).
0022-3697/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jpcs.2004.04.002

Li0.5Fe2.5O4. Experimental data indicates that these excess

Li ions occupy tetrahedral A sites, giving a formula
(Fe1.020.5xLi0.5x)A(Fe1.52xLi0.5Tix)BO4. XRD [10,11] shows
that substitution is ordered giving a space group P4332 for
0 # x # 0:4: The lattice constant increases only very
slightly over this range from 0.833 to 0.834 nm for powder
samples. 57Fe Mossbauer spectra of Ti-doped lithium ferrite
with the value of x in this range (11 and work in our own
laboratory) show two sextets corresponding to iron on the
A and B sites, respectively. The average hyperfine field for
both sextets is reduced relative to that for lithium ferrite
indicating substitution on both sub-lattices. Fe3 spins on
the B sites are ferromagnetically coupled to each other as
are the spins on the A sites. Fe O Fe exchange, however,
couples spins on A and B sites antiferromagnetically.
The overall magnetisation of undoped lithium ferrite is due
to the excess of Fe3 ions on octahedral sites over those on
tetrahedral sites. Magnetisation of the Ti-doped lithium
ferrite is lower than that of the undoped ferrite suggesting
greater substitution on B sites than on A sites [8].
In this paper we use interatomic potential and ab initio
calculations to investigate the stability of the proposed
substitution pattern in Ti-doped lithium ferrite with low
concentrations of Ti relative to other possible defect
structures and gain insight into the factors determining
this distribution.

1664

H.M. Widatallah, E.A. Moore / Journal of Physics and Chemistry of Solids 65 (2004) 16631667

2. Computational procedure
2.1. Interatomic potential calculations
Interatomic potential calculations were carried out using
the program GULP [12] in which the force field used consists
of a pairwise interaction energy that is composed of a
Buckingham potential to model the short-range Pauli
repulsion and the leading term of any dispersion energy
and the Coulomb interaction, such that


2rij
qq
Eij A exp
2 Crij26 i i
r
rij
where Eij is the interatomic potential, A; r and C are
empirical constants, q is the charge of the particles and rij
the interatomic spacing. GULP uses the Mott Littleton
approach to point defect calculation with the crystal
surrounding the defect divided into three spherical regions.
In the first region, all the ions are treated exactly and are
allowed to relax their positions in response to the defect.
. In a second
The radius of this region was taken to be 8 A
spherical region, individual ions were displaced, and the
ions in a harmonic potential well were assumed to
approximate the response to the electrostatic force of the
.
defect. The radius of the second region was set to 14 A
In the third region, a similar approximation is used except
that only polarisation of sub-lattices is considered.
The interatomic potential parameters for Li, Fe3 and
O22 used are similar to those used [13] to investigate
quaternary Li Mn Fe O spinels. The O O potential
parameters are identical to those in an earlier paper [14]
and therefore the Ti4 parameters given there are used.
The parameters used are given in Table 1.
2.2. Ab initio calculations
Ab initio calculations were carried out using the program
CRYSTAL 98 [15]. This code is based on the ab initio periodic

linear combination of atomic orbitals. An unrestricted

Hartree Fock treatment was employed. Because of the
large size of the unit cell (the unit cell of lithium ferrite is
Li4Fe20O32), a basis set in which the core electrons were
Table 1
Interatomic potentials used in this work
A /eV

r /A

described by Poples 3-21G basis [16] was used. For the

valence electrons a larger set of functions was used based on
the 8-6-411G(Fe, Ti) or 8-5G (O) basis sets used in CRYSTAL
calculations on iron and titanium oxides by other workers
[17,18]. These valence basis sets were reoptimised for the
3-21G description of the inner electrons by varying the
coefficients using GAMESS [19] calculations on Fe3 and
Ti4. For Li we used Poples 3-21G basis set, but with the
outer s/p shell replaced by a p function of coefficient 0.6.
This approach has been used successfully for calculating
electric field gradients [20]. The Fe and O basis sets were
tested on a-Fe2O3. The experimental order of energies of the
possible spin states of this oxide (ferromagnetic and the three
possible antiferromagnetic states) were reproduced correctly
for the experimental geometry. We also performed runs on
a-Fe2O3 for different values of the lattice parameter c; but a
fixed c=a ratio and for several values of c=a for a fixed value of
a: For the experimental c=a ratio of 2.7336, our calculations
gave a minimum around c 1:381 nm compared to the
experimental value 1.3772 nm. For a 0:5069 nm, our
minimum ratio, c=a was 2.727. The agreement with
experiment is reasonable and comparable to that obtained
using large basis sets and so gives us confidence in our basis
set. The basis sets are given in Table 2.

3. Results
3.1. Interatomic potential calculations
As Ti4 ions are the minority species, we considered
models in which these ions were present as defects in
Li0.5Fe2.5O4. Both models in which Ti4 substitutes for an
Fe3 ion or Li ion and those in which Ti4 ions are present
in interstitial sites were considered. Li and Fe3 vacancies
and excess Li substituting on Fe3 sites were considered as
balancing defects. Both substitution and vacancy formation
will reduce the number of magnetic ions in agreement with
the experimental results. Reduction of Fe3 to Fe2 was not
considered as there is no experimental evidence for the
presence of Fe2. The defect reactions considered are given
below using the Kroger Vink notation.
TiO2 s FexFe LixLi ! TizFe V0Li 1=2Li2 Os
1=2Fe2 O3 s

6 Spring
C/eV A
Shell
constant
charge/e
22
k /eV A

Li core-O22 shel
479.837 0.3
0
22
Fe3
shel 1342.754 0.3069 0
oct shel-O
22
Fe3
shel 1240.232 0.3069 0
tet shel-O
Ti4 shel-O22 shel 2088.107 0.2888 0
O22 shel-O22 shel
22.410 0.6937 32.32
Fe3 core-Fe3 shel
O22 core-O22 shel

TiO2 s 4=3FexFe ! TizFe 1=3V000

Fe 2=3Fe2 O3 s

1
2

TiO2 s 3=2FexFe 1=4Li2 Os ! TizFe 1=2Li00Fe

3=4Fe2 O3 s

zz
TiO2 s 2FexFe OxO ! TizFe V000
Fe VO Fe2 O3 s 4

10082.50
20.53

1.029
2 2.513

TiO2 s FexFe LixLi ! TizzzLi V000

Fe 1=2Li2 Os
1=2Fe2 O3 s

H.M. Widatallah, E.A. Moore / Journal of Physics and Chemistry of Solids 65 (2004) 16631667
Table 2
Exponents and coefficients of the contracted Gaussian-type basis functions
used in the ab initio calculations
Type

Exponent

TiO2 s 3=2FexFe LixLi 1=4Li2 Os ! TizzzLi 3=2Li00Fe

3=4Fe2 O3 s

Coefficient
s

1665

TiO2 s 4LixLi ! TizzzLi 3V0Li 2Li2 Os

000
0
TiO2 s FexFe LixLi ! Tizzzz
int VFe VLi 1=2Li2 Os

Fe
s

sp

sp

sp
sp
d

1=2Fe2 O3 s
3299.184
499.0886
109.1614
143.4652
31.16858
9.483612
9.464565
3.100373
0.986493
1.314
0.532

0.06358590
0.3762016
0.6817845
20.1105517
0.0968468
0.9587974
20.2920555
0.3375236
0.8519416
1.0
1.0

TiO2 s

0.0583
0.2591
0.5162
0.5656
1.0

Ti
s

sp

sp

sp
sp
d

2335.020
353.0442
77.05846
99.57387
21.54671
6.413965
6.238379
1.996108
0.06464899
1.017186
0.758559

0.06421661
0.378412
0.67968
20.109471
0.1019427
0.9546224
20.2861372
0.3218278
0.8595511
1.0
1.0

0.1372966
0.5458753
0.4890681
0.01923665
0.4404422
0.6356195
1.0
1.0

6.141248
2.453525
0.952059
0.496983

sp
p

36.8382
5.48172
1.11327
0.540205
0.102255
0.6

0.161546
0.915663
1.0

O
s

sp
sp
d

0.0592394
0.3515
0.707658
20.404453
1.22156
1.0

The results are given in Table 3.

Defect reactions involving interstitial Ti4 were not very
favourable. Defect reactions involving substitution of Ti for
Fe were more favourable. Substitution of Ti4 on an
octahedral Fe3 site was much more favourable than
substitution on a tetrahedral Fe3 site. However, Li also
showed a preference for octahedral sites, although the
energy difference between substitution on octahedral and
tetrahedral sites was smaller than that for Ti4. The lowest
energy defect reaction was reaction (3) with both Ti and Li
replacing Fe on octahedral B sites. This would lead to a
large drop in magnetisation and would not agree with
the observed changes in the Mossbauer spectrum on both

Defect energy (eV)

Reaction (1)

Ti4 on B site
Ti4 on A site

21.56
0.52

Reaction (2)

Ti4 on
Ti4 on
Ti4 on
Ti4 on

B site, vacancy on B site

B site, vacancy on A site
A site, vacancy on B site
A site, vacancy on A site

21.84
21.25
0.23
0.82

Reaction (3)

Ti4 on
Ti4 on
Ti4 on
Ti4 on

B site, Li on B site
B site, Li on A site
A site, Li on B site
A site, Li on A site

22.44
22.36
20.37
20.29

Reaction (4)

Ti4 on
Ti4 on
Ti4 on
Ti4 on

B site, vacancy on B site

B site, vacancy on A site
A site, vacancy on B site
A site, vacancy on A site

1.21
2.99
3.28
5.06

Reaction (5)

Vacancy on B site
Vacancy on A site

3.47
5.25

Reaction (6)

Li on B site
Li on A site

1.68
1.92
4.33

Reaction (7)
322.037
48.4308
10.4206
7.40294
1.5762
0.373684
0.8

2=3Fe2 O3 s

Defect reaction

0.048967
0.146523
0.302947
1.0

0.0696686
0.381346
0.681702
20.263127
1.14339

4=3V000
Fe

Table 3
Defect energies for reactions (1)(10)

Li
s

8
Tizzzz
int

00
TiO2 s 2FexFe Li2 Os ! Tizzzz
int 2LiFe Fe2 O3 s 10

0.1411006
0.5603874
0.4676444
0.02376201
0.4689113
0.6083113
1.0
1.0

30.48
8.692
3.101
1.171
0.4298

4=3FexFe

0.244586
0.853955
1.0
1.0

Reaction (8)

Vacancy on B site
Vacancy on A site

8.57
10.35

Reaction (9)

Vacancy on B site
Vacancy on A site

8.28
10.65

Reaction (10)

Li on B site
Li on A site

5.90
6.22

1666

H.M. Widatallah, E.A. Moore / Journal of Physics and Chemistry of Solids 65 (2004) 16631667

A and B sites. For defect reaction (3), we also ran

calculations on supercells of formula Li5.25Fe16.25Ti2.5O32
corresponding to x 0:3125 in Li0.50.5xFe2.521.5xTixO4
with both Fe A and B sites partially occupied by Fe and by
Ti and/or Li to represent random occupation according to
the possible patterns of substitution over A and B sites.
The supercells were optimised. With Fe and Li only on B
sites the lattice parameter, a; was reduced from 0.8314 nm
in pure lithium ferrite to 0.8263 nm. With Ti on B sites and
Li on A sites, the lattice parameter suffered a smaller
reduction (0.8299 nm) and the optimised cell had lower
energy. Experimentally, the Ti-doped lithium ferrites show
a small increase in lattice parameter from 0.833 to 0.834 nm
for x 0 ! 0:4: Thus, the supercell with Ti on A sites and
Li on B sites produced closer agreement with experiment.
Our initial calculations were for isolated defects, but the
supercells include contributions from defects in close
proximity as well as isolated defects. We therefore
considered clusters of defects corresponding to reaction
(3). Particularly, an energetically favourable cluster
(defect energy 2 5.76 eV) was found with two Ti4
substituting for Fe3 on B sites and one Li substituting for
Fe3 on an A site and with all three substituting ions linked
to a common oxygen. The position of this defect in the unit
cell is shown in Fig. 1.
A cluster with all substitution on B sites had a defect
energy of 2 3.53 eV. These results suggest that substitution
of Li for Fe on a tetrahedral A site is favoured by the
formation of defect clusters in which the Li is linked
through a common oxygen to two Ti4 on octahedral B sites.
3.2. Ab initio calculations
Calculations were performed on supercells Li5Fe17Ti2
O32 corresponding to x 0:25 in the formula Li0.50.5x

Fig. 1. Two unit cells of Ti-doped lithium ferrite showing position of cluster
of two Ti and one Li atoms. The black spheres are Fe ions, the largest grey
spheres are Ti ions and the small grey spheres with no bonds shown are Li
ions. The cluster consists of the two Ti ions in the centre of the figure and
the Li ion on the right above these two. The c axis of the cell is vertical.

Fe2.521.5xTixO4 formed by substituting for three Fe3 ions in

the unit cell of lithium ferrite by two Ti4 ions and one Li
ion. The ordered structure of lithium ferrite [20] was used.
In case the results were affected by changes in lattice
parameter, we ran all substitution patterns at two values of
the lattice parameter, a; 0.8314 and 0.833 nm,
corresponding to the values found for single crystal and
powder X-ray diffraction determinations of the structure.
The results for various patterns of substitution on the
A and B sites are given in Table 4.
The order of the energies is the same for both lattice
parameters. In contrast to the interatomic potential calculations, the supercell in which both Ti4 and Li substitute
on B sites is the least favourable. This may be due to the
reduced spin interactions as spin spin interactions enter
into these calculations, but are ignored in interatomic
potential calculations. However, despite maximising the
unpaired spin giving an advantage when the defects are
relatively isolated (see highest energy for each spin state),
the formation of the cluster in which Li on an A site and
two Ti4 on B sites are linked through a common oxygen
again produces the lowest energy.

4. Discussion
Interatomic potential calculations indicated that as
isolated defects, Ti4 and Li substitute for Fe3 ions on
octahedral B sites. This is not surprising as Ti4 is known to
favour octahedral sites in other doped iron oxides and Li
occupies octahedral sites in lithium ferrite itself. However, a
cluster of two Ti4 ions on B sites and one Li ion on a
tetrahedral A site was found to stabilise the structure of the
Ti-doped lithium ferrite. This concentrating of the defects in
one part of the unit cell reduces disruption in the cell,
for example giving only a small change in lattice parameter.
The ab initio calculations took into account not only
structural factors as in the interatomic potential calculations,
but also changes in spin interactions on substitution. In the
ferrites, spins on Fe3 ions on the A sub-lattice are
ferromagnetically coupled to each other as are the spins on
the B sub-lattice. Ions on the A and B sub-lattice are
antiferromagnetically coupled via exchange FeA O FeB.
In lithium ferrite Li0.5Fe2.5O4, the calculated a b population
is higher on the B sites (4.697) than the A sites (2 4.660) and
the overlap Fe O population is positive for both sites with
stronger bonding of the A sites to a electrons and the B sites
to b electrons. In the Ti-doped lithium ferrite, the average
calculated a b population on the B sites shows a small drop
to 4.688 and that on the A sites a small increase to 2 4.663.
This would produce a small drop in the A-site magnetic field
and a small increase in the B-site magnetic field, but the effect
of substituting non-magnetic nuclei on both sites will cause a
much larger reduction in both fields. The larger hyperfine
field and isomer shift for Fe in octahedral sites than in
tetrahedral sites in the undoped lithium ferrite has been

H.M. Widatallah, E.A. Moore / Journal of Physics and Chemistry of Solids 65 (2004) 16631667

1667

Table 4
Ab initio calculated energies of Li5Fe17Ti2O32 for different distributions of substituted Ti4 and Li
Li site

A
B
A
A
A
B
B
B

Ti4 site

A
A
B
B
A/B
A/B
A/B
B

A/B linkage

Both A linked to B
A linked to one B
A and B linked to common O
Both A linked to B
Both B linked to A
A and B linked to common O

explained as due to the more covalent character of the Fe O

interaction at the tetrahedral sites. Our calculated overlaps
show that this difference in covalency is maintained in the
doped ferrite with the Fe O overlap population remaining
similar to that in the undoped ferrite, but with a slight increase
for Fe atoms close to the defect region. The Li O overlap for
both a and b electrons is markedly larger than the Fe O
overlap. Spin interactions appear to play a role in stabilising
substitution on tetrahedral sites by favouring states with
higher numbers of unpaired spins. However, the determining
factor in the cation distribution appears to be structural. Ab
initio calculations agree with the interatomic potential
calculations in finding that a defect cluster of two Ti4 ions
on octahedral sites and an Li ion on a tetrahedral site
stabilises the Ti-doped structure.
It is interesting to note that the formation of clusters has
been put forward to explain the Mossbauer spectra of
Li0.50.5xFe2.521.5xTixO4 with x 0:5 and 0.7 [11] and
the temperature-dependence of the spectra of Mg Ti
ferrites [21].

5. Conclusions
Both interatomic potential calculations and ab initio
calculations indicate that Ti-doped lithium ferrite of formula
Li0.50.5xFe2.521.5xTixO4 with low concentrations of Ti is
stabilised by the formation of defect clusters of two Ti4
ions substituting for Fe3 on B sites and one Li ion
substituting for Fe3 on an A site. In these clusters both Ti4
ions and the Li ion are linked through a common oxygen. It
is suggested that such a cluster is stable because it causes
little disruption to the structure of the unit cell.

Acknowledgements
We thank The Abdus Salam International Centre for
Theoretical Physics (ICTP) Trieste for support (HMW) and

Unpaired spins
per unit cell

35
25
15
15
25
15
15
5

Energy (104 eV)

a 0:8314 nm

a 0:833 nm

22.54781005
22.54780962
22.54781444
22.54781834
22.54781510
22.54780690
22.54781092
22.54780096

22.54780779
22.54780731
22.54781213
22.54781603
22.54781282
22.54780458
22.54780860
22.54779929

the UK computational chemistry working party for a grant

of time on the EPSRC superscalar facility at the Rutherford
Appleton Laboratories.

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