Khachaturyan 1985

Progress in Materials Science Vol. 29, pp. 1-138, 1985 0079-6425/85 $0.00 + .
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Printed in Great Britain. All rights reserved Copyright © 1985 Pergamon Press Ltd
CONCENTRATION WAVE APPROACH IN

STRUCTURAL A N D THERMODYNAMIC
CHARACTERIZATION OF CERAMIC CRYSTALS
A. G. Khachaturyan* and B. L Pokrovskiit

*Institute of Crystallography, Academy of Sciences of the USSR, Moscow, USSR
tChemical Department of Moscow University, Moscow, USSR
CONTENTS
PREFACE 2
INTRODUCTION 3
1. CONCENTRATIONWAVE REPRESENTATION OF THE STRUCTURE OF INORGANIC COMPOUNDS 4
1.1. Representation o f Completely Ordered Phases in Terms of Static Concentration Waves 4
1.2. Concentration Waves and Diffraction 7
2. STABILITY OF STOICHIOMETRIC COMPOUNDS 10
2.1. Concentration Wave Representation o f the Configurational Energy of a Chemical Compound 10
2.2. The Maximal Amplitude Principle and Dominant Waves 12
2.3. Stability of Layer Structures 15
2.4. The Most Stable Layer Structures with Fixed Stoichiometry 17
2.5. The Nature of Homologous Series of Chemical Compounds 20
2.6. Stability o f a Host Lattice with Respect to Intracrystalline Field at Its Sites Produced by
Ordered Interstitial Atoms 30
2.7. Host Atom Displacements Induced by Interstitial Ordering 35
2.8. Secondary Ordering in Nonstoichiometric Compounds 40
3. STABLE STRUCTURES OF TRANSITIONALMETAL OXIDES BASED ON THE BCC HOST LATTICE
FORMED BY OXYGEN ATOMS 41
3.1. Interaction of Interstitial Atoms in the bcc Host Lattice 41
3.2. Interstitial Superstructures in the bcc Host Lattice. Titanium Oxides 43
3.2.1. Host lattice instability produced by secondary ordering (3.2.46) 53
3.2.2. Formation o f the NiAs type structure 55
3.2.3. Tertiary ordering resulting in the rutile structure 55
3.3. Alternatives to the Rutile Structure: the o~-PbO2 and Corundum Structures 58
3.3.1. Even numbers of s l 61
3.3.2. Odd numbers o r s I 65
3.3.3. The case of s I = 3. The corundum structure 67
3.4. The bcc Lattice-Based Homologous Series of Titanium and Vanadium Oxides 70
3.4.1. Derivation o f stoichiometric formula for homologous series 70
3.4.2. Sequence o f filled and vacant planes in homologous layer phases, MnOEn_I 72
3.4.3. Determination o f alternating plane indexes 72
3.4.4. Mutual positioning of interstitial Ti atoms in the 0 x and Oy sublattices 75
3.4.5. An example: the structure of the TisO9 phase 76
3.4.6. Summary 77
4. STABLE CERAMIC COMPOUNDS BASED ON THE FCC HOST LATTICE 79
4.1. Interaction of Interstitial Atoms in Tetrahedral Interstices of the fcc Lattice 81
4.1,1. The characteristic matrix in the case of tetrahedral interstice occupancy 81
4.1.2. Eigenvalues and eigenvectors of the characteristic matrix 82
4.1.3. Intracrystalline field along fcc host lattice sites 84
4.2. Primary Interstitial Superstructures with Fixed Stoichiometry in Tetrahedral
Interstices o f the fcc Host Lattice 85
4,2.1. Atomic structure of the minimum eigenvalue related to k o = (000) 87
4.2.2. Atomic structures of the minimum eigenvalue related to the {100} star 88
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2 PROGRESS IN MATERIALS SCIENCE
4.2.3. Structures obtained by refinement o f the model 91

4.2.3.1. Stable structures generated by the star {½ 1 0} 92
4.2.3.2. Stable structures generated by the star (,¢1
7 a7 ~,
71 95
4.2.3.3. Oxides generated by the star {~ ~13} 100
4.2.4. Conclusion 101
4.3. Secondary Interstitial Superstructures in Tetrahedral Interstices of the fcc Host Lattice 101
4.3.1. The characteristic matrix 102
4.3.2. Secondary superstructures based on the primary superstructures of the CuO
and PbO types generated by the star { 100) 103
4.3.3. Secondary superstructures based on the primary Cu20-type superstructure
generated by the star {100} (pyrochlore, sheelite ) 104
4.3.3.1. Pyrochlore-type structure 108
4.3.3.2. Crystobalite structure 109
4.3.3.3. Sheelite and zircon structures 111
4.4. Interaction of Interstitial Atoms Occupying Octahedral Interstices of the fcc Host Lattice 111
4.5. Primary Interstitial Superstructures with Fixed Stoichiometry Formed by Ordering
of Interstitial Atoms over Octahedral Interstices of the fcc Host Lattice 114
4.6. Secondary Superstructures Formed by Combined Ordering of Interstitial Atoms in
Octahedral Interstices and Vacancies in the fcc Host Lattice 117
4.6.1. Homologous phases M,03~ l 120
4.6.1.1. Stoichiometricformula 120
4.6.1.2. The generating plane 122
4.6.1.3. The sequence of alternating planes 122
4.6.1.4. Observation results 123
4.7. Spinel as a Superstructure Based on Occupation of Octahedral and Tetrahedral
Interstices of the fcc Host Lattice 124
4.7.1. The interaction energy of atoms occupying octahedral interstices 128
4.7.2. Stability of the spinel structure in the case of ionic binding 128
5. CONCLUSION 133
ACKNOWLEDGEMENTS 137
REFERENCES 137
PREFACE
This review will provide an account of the new approach to the theoretical determination of
the structure of some ceramic compounds. It is an extension of the previous survey on
ordering in substitutional and interstitial solid solutions. (1) We shall reformulate here the
concentration wave concept used in the statistical thermodynamics and crystallography of
order-disorder transformations and then apply it to new situations, namely stoichiometric
ceramic compounds. Indeed, the method of concentration waves is known to have made
substantial advances in the understanding of the symmetry aspects of order-disorder
transformations, to take into consideration long-range interactions in an alloy and to predict
the structure of an ordered phase from a knowledge of the set of interatomic interaction
energies. Recent extensions of this approach are also efficient in determining the stable
structures of stoichiometric ceramic compounds, for a ceramic compound structure may be
regarded as a completely ordered substitutional or interstitial superstructure based on one
of the simple host lattices, bcc, fcc or hcp.
The ceramics structure determination, however, requires some extension of the concen-
tration wave formalism, viz. the introduction of a stability criterion which is referred to as
the maximal amplitude principle.
The survey includes a general formulation of the concentration wave concept and the
maximal amplitude principle, its applications to the structure determination of metal oxides
based on the bcc host lattice (TiO2, ~-PbO2, corundum, the Ti,O:, 1 series, etc.), of oxides
based on the fcc host lattice with octahedral and tetrahedral occupancies (the structures, CuO,
Ag20, As203, 5e203, Sc4Ti3012, pyrochlores, crystobalite SiO2, CoWO4, CaTiOa, the Magneli
phase series Mo,O3, 1, etc., and a discussion of the spinel structure stability.
CHARACTERIZATION OF CERAMIC CRYSTALS 3
The review is addressed to graduate students and researchers in physical metallurgy,

ceramics, solid state chemistry, crystal chemistry and solid state physics. To follow the
discussion, it is sufficient to have elementary knowledge in mathematics and crystallography.
INTRODUCTION
The field to be covered in this review is the theoretical determination of the structure of some
ceramic compounds, based on the knewledge of the set of interatomic potentials. The
structure can be determined directly by testing an infinite number of various atomic
configurations and choosing the only one which provides the free energy minimum. In reality,
this approach can hardly be successful since the computer load would be beyond the means
of today's high speed computers. Fortunately, there is another way to solve the problem.
It should be remembered that regardless of their complexity most inorganic crystal
structures can be interpreted as interstitial-substitutional superstructures built up on the basis
of one of simple high-symmetry host lattices, fcc, bcc or hcp. Indeed, atoms and their
vacancies can be related to several systems of points in the fcc, bcc or hcp host lattice to within
small atomic displacements and homogeneous distortion. In other words, the structure of a
compound can be interpreted in terms of the Ising model in which the fcc, bcc or hcp lattices
serve as a framework for ordered distribution of substitutional and interstitial atoms and their
vacancies.
For instance, the spinel structure, MgA1204, may be considered as a completely ordered
interstitial superstructure based on the fcc host lattice framework formed by oxygen atoms,
interstitial atoms, Mg and A1, being regularly distributed in octahedral and tetrahedral
interstices of the fcc host lattice, respectively (for details see Section 4.7).
This Ising model approach enables one to employ the modern developments in the
statistical mechanics of ordered alloys, in particular the method of static concentration waves
proposed by one of the authors. ~2-6)The concentration wave method enables us to take into
account the arbitrary long-range interatomic interaction which is not possible with the
conventional approach. It also allows us to determine the atomic structures of stable oxides
and other ceramic compounds from a quite simple interatomic interaction model. These
developments of the theory proved to be possible since the method of concentration waves
formulates the structure determination problem in terms of the reciprocal lattice through the
analysis of concentration waves amplitudes which are, on the one hand, structure amplitudes
of the superlattice reflections and, on the other hand, long-range order parameters. The
conce~ltration wave apprcach enables one to reveal the profound relations between the
structure amplitudes, reciprocal lattice geometry and thermodynamic stability of ceramic
crystals, and to build a model which combines thermodynamics and crystallography of many
compounds.
We shall demonstrate how this method predicts the crystal structure of the main oxide
ceramics in the particular case of stoichiometric completely ordered compounds which do not
undergo disordering below the melting temperature (the order-disorder temperature is much
higher than the melting temperature). Room temperature can be then treated as low. We shall
introduce a new kinematic requirement to the ordered phase stability, to be referred to as
the maximal amplitude principlefl) It will be shown that the maximal amplitude principle
combined with a simple model of interatomic interaction determines the atomic structure of
stable transitional metal oxides with fixed stoichiometry and the structure of homologous
series of oxides with variable valency of metal atoms.
1. CONCENTRATION WAVE REPRESENTATION OF THE STRUCTURE OF INORGANIC

COMPOUNDS
1.1. Representation of Completely Ordered Phases in Terms of Static Concentration

Waves
We will now describe the basic concepts of the concentration wave approach as applied
to fully ordered atomic distributions which form the structure of stoichiometric compounds.
For specificity, we shall confine ourselves to discussing binary interstitial compounds built
as a completely ordered interstitial superstructure though the results can be readily extended
to more complex systems.
Let the number of interstitial atoms be less than that of interstices which are denoted by
the indices (p, R) where the vector R labels the host lattice unit cell center and the integer
p, the position within the unit cell (in multicomponent compounds p may also denote the kind
of atoms). Therefore the indices (p, R) give the "address" of the interstice where interstitial
atoms may be observed. We will assume that all the positions, p = 1, 2 . . . . v, are crystal-
lographically equivalent, that is they can be brought in coincidence by applying the host
lattice symmetry operations (here v is the position multiplicity). Any distribution of atoms
over sites {p, R } is then described by the probability n(p, R) to find an interstitial atom in
position (p, R).
In a fully ordered state the deterministic situation in which each site is either definitely
occupied or vacant exists. The probability distribution function then is either unity or zero,
respectively. Any distribution n(p, R) may be written as a superposition of static concen-
tration waves (Fourier series)
n(p, R) = ~ a(p, k) exp(i2rckR) (1.1.1)

k
where a(p, k) is the amplitude of the concentration wave exp(i2rckR) modulating the
distribution of interstitial atoms over the p-th Bravais sublattice formed by translating an
interstice of type p ; 2nk is the wave vector defined within the first Brillouin zone of the host
lattice.* The relationships between coefficients a(p,k) determine the function n(p,R)
symmetry with respect to rotations and reflections and thus the symmetry of the super-
structure described by the function n(p, R).
The reality of n(p, R) is insured if the relation
a(p, k)* = a(p, - k ) (1.1.2)
between amplitudes corresponding to the wave vectors k and - k holds.
Since eq. (1.1.1) is a Fourier series in which the amplitudes a(p, k) are Fourier coefficients,
the amplitudes a(p,k) may be represented through the usual equation for the Fourier
coefficients:
1 ~ n(p, R) exp(-i2nkR).
a(p, k) = -~o (1.1.3)
It follows from eq. (1.1.3) where the summation is carried out over No sites {R} of the host
Bravais lattice, that
! ~ n(p, R) = No
a(p, O)= -~o Np = c, (1.1.4)
*For brevity, the term wave vector will denote the vector k.
where Np = Y-s n (p, R) is the number of interstitial atoms in the p-th sublattice, cp the fraction
of interstices of the p-th sublattice occupied by interstitial atoms. Separating out the zeroth
term depending on k = 0 and in the light of eq. (1.1.4), one may rewrite eq. (1.1.1) as
n(p, R) = cp + ~' a(p, k) exp(i2r~kR) (1.1.5)

k
where the prime means that the term depending on k = 0 is left out of the sum.
Equations (1.1.1) and (1.1.5) show that the distribution n(p,R) is described by the
superposition of v concentration waves, one per each sublattice p.
The other, sometimes more convenient, description of n(p, R) may be obtained by using
normal concentration waves,
~P~k(P, R) = o~(p, k) exp( i 2~k R ) (1.1.6)
where v~(p, k) = (v~(1, k), u~(2, k) . . . . v,(v, k)) is a generalized vector in the v-dimensional
space of the interstitial sites which characterizes the "polarization" of the plane wave
exp(i2nkR), i.e. contribution of this wave into the modulation of atomic distribution over
the p-th sublattice, the index ~ (t7 = 1, 2 . . . . . v) denotes the "polarizations" related to the
wave vector, k.
Therefore, each normal concentration wave (1.1.6) is completely determined by the indices
(~, k).
What is remarkable is the profound analogy between the concentration waves and normal
crystal lattice vibrations. The normal vibrations of a Bravais crystal lattice are described by
the functions
(P~k(J', R) = e~(j, k) exp (i 2rckR ) (1.1.7)
where G(k) = (G(1, k), e,(2, k), G(3, k)) is the unit polarization vector, j = (1, 2, 3) is the
Cartesian coordinate index which plays here the part of the index p in (1.1.6). One may readily
see that the function (1.1.7) is formally analogous with the function (1.1.6). The reason for
this is that the complete set of the orthonormal functions (1.1.6) induces the irreducible
representations of the space group of the host lattice. The set of orthonormal functions satisfy
the following equations
1 v
,~--i ~ ~P,k(P, R)tp*k,(p, R)-- 6,~'Jkk, (1.1.8)
where 6~,, and 6kk' are Kronecker symbols. It is obvious that eqs (1.1.8) hold if the
orthogonality equations
~, v~(p, k )v*(p, k') = 6o~'rkk' (1.1.9)

p=l
for the "polarization vectors" v~(p, k) are fulfilled. Making use of the complete set of normal
concentration waves (1.1.6), one may find the representation of the density function, n (p, R),
an alternative to the representation (1.1.1). It has the form
n(p, R) = ~ ?~(k)~p~k(p, R) = ~ ?~(k)v~(p, k)exp(i2rrkR) (1.1.10)

a,k o,k
where ?~(k) are amplitudes of normal concentration waves. Comparing eqs (1.1.1) and
(1.1.1 O) one may find the relations between amplitudes, a (p, k) and 7~(k). They have the form
a ( p , k ) = y' ?,(k)u~(p,k). (1.1.11)

cr=l
Above we have emphasized the close similarity between normal crystal lattice vibrations and
normal static concentration waves. However, apart from this similarity, there are essential
distinctions. Unlike crystal lattice vibrations, the superposition o f normal concentration
modes describes the discrete function n(p, R) which, by definition, can be either 0 or 1.
Consequently, the amplitudes, 7,(k), entering (1.1.10), unlike amplitudes of normal vi-
brations, are not independent variables. There are certain relations between them.
To find some of these relations one should recall that the function, n(p, R), equal either
to zero or unity being raised to any power, s, is identically equal to itself:
(n(p, R)) s = n(p, R) (1.I. 12)
Assuming s = 2 in eq. (1.1.12) and employing the representation (1.1.10), we have
~ y,,(k,)oo,(p, kl) ~,,(kz)o~,,(p, kz) exp(i2r~(k, + kz)R)

~r',a" kl,k2
-= ~ 7 o ( k ' ) o , ( p , k ' ) e x p ( i 2 r c k ' R ) . (1.l.13)
Or,k"
One m a y see that raising n(p, R) to power 2 results in appearance in the left hand side of
eq. (1.1.13) of new exponentials of the kind of exp(i2n(k~ + k2)R) with a new wave vector
kl + k2.
The identity sign in eq. (1.1.13) means that the same exponential characterized by the wave
vector
k' = kt + k2 (1.1.14)
should enter the right hand side of (1.1.13) and thus, the distribution (1.1.10).*
Therefore, we arrive at the conclusion that the sum of any two wave vectors in the
distribution (1.1.10) should be equal to either one of the wave vectors entering (1.1.10) or
zero to within a reciprocal lattice vector H of the host lattice.
This criterion, with an accuracy to the above constraint, has in fact a wider range of
applicability. It is valid for partially ordered phases as well.
The other relation between amplitudes y , ( k ) is given by the summation rule
Y~ I~,,(k)l:- c (1.1.1s)
o,k
where
C ~ - E c p = g i n t / g O,
p
gint-~" E n(p, R ) (1.1.16)
p.g
is the total number of interstitial atoms. To prove the summation rule (1.1.15), we shall use
in the definition of c the identity (n(p, R ) ) 2 =n(p, R) following from (1.1.12) at s = 2:
1 1
C = "Vop,RwEn(p, R) = No E n2(p, R ) . (1.1.17)
, p,R
*Exceptions are quite special particular cases where coefficientsat the exponential exp(i2nk'R) on the left hand
side of eq. (1.1.13) prove to be equal to zero because of special features of the amplitudes 7,(k) and vectors k~ and
k2. These cases will be discussed below in Section 2.4 [see eq. (2.4.8)].
Substituting (1.1.10) into the right-hand side of eq. (1.1.17) and bearing in mind the
orthogonality conditions (1.1.8) one has
1 ~ nZ(P' R) =
c = Noo ~0~ * ' )~o~,k,(p,
E ?,(k)q~,k(p, R) Z ?~,(k * R)
p,R , o,k a',k'
= ~,gTk?,(k)?*,(k') No p,, q~,k(P, R)q~k, (p, R)
t ,
(1.1.18)
aa'kk' a,k
The chain of equalities (1.1.18) proves the summation rule (1.1.15).
1.2. Concentration Waves and Diffraction

One of the advantages of describing an ordered structure in terms of concentration waves
is the very simple and direct relation between the concentration waves and the diffraction
pattern. It will be shown below that each concentration wave generates its own set of
superlattice diffraction reflections separated by fundamental reciprocal lattice vectors. The
number of such sets is equal to that of concentration waves in eq. (1.1.1). This conclusion
will be proved below for the particular case of elastic kinematic scattering by a binary
interstitial phase.
According to the kinematic theory of scattering, the amplitude of the plane wave scattered
by an atom can be represented as
f (q ) exp( - iqr ) (1.2.1)
where r defines the coordinates of the atom with respect to the origin, q is the diffraction
vector equal to the difference of the wave vectors of the scattered and incident waves and
f ( q ) is the atomic scattering factor of the atom.
Let the binary crystal have a Bravais host lattice whose sites are occupied by host atoms
and interstices denoted by the indices, p = 1, 2 . . . . . v, are occupied by interstitial atoms. In
this case the summation of amplitudes (1.2.1), scattered by each host atom, results in the total
amplitude
Ahost(q) =~fhost(q)exp(--iqr) =fhost(q)~exp[--iq(R + u(R))] (1.2.2)

v R
scattered by the entire host lattice. Here r = R + u(R), R labels the sites of the ideal host
lattices, u(R) is displacement of the host atom from its site R, and fhost(q) is the atomic factor
of a host atom. The summation in eq. (1.2.2) is carried out over all host lattice sites.
The amplitude scattered by interstitial atoms forming the ordered distribution is
Ai,t(q) = ~ f, nt(q) exp(- iqr) (1.2.3)

r
where fint(q) is the atomic factor of an interstitial atom and r is the vector denoting the
interstices occupied by an interstitial atom. The summation in eq. (1.2.3) is taken over all
interstitial atoms. The vector r defining the interstitial atom positions in eq. (1.2.3) can always
be represented as
r = R + hp (1.2.4)
where p = 1, 2 . . . . . v; hp is the distance from the host lattice site to the nearest interstice of
the p-th kind. Since the distribution function n(p, R) takes on the value 1 if the interstice
(p, R) is occupied and 0 otherwise, one may rewrite eq. (1.2.3) in terms of the function
n(p, R):
aint(q ) = E fint(q )rt (p, R ) e- ~q(R+ hp

p,R
=fint(q) ~ e-'hp~ n(p, R) e -iqR. (1.2.5)

p=l R
where the summation is carried out over all host lattice sites, R.
The total scattering amplitudes is the sum of (1.2.2) and (1.2.5):
The scattered intensity at the point q of the reciprocal space is known to be equal to the
squared modulus of the total scattering amplitude, i.e.
I(q) ---IA(q)12. (1.2.7)
Neglecting for simplicity the host atom displacements in eq. (1.2.6) yields
A(q) =Ao~t E e-i'*+fi.t ~ e-'. E n(p, R) e -'R (1.2.8)

R p=l R
The first term in eq. (1.2.8) is easily seen to be non-zero only in the fundamental reciprocal
lattice points. Indeed,
~'fhostN0 if q = 2nil
Ahost(q) = fhost ~ e-MR (1 . 2 . 9 )
to otherwise
where H is a fundamental reciprocal lattice vector. Therefore, the second term in eq. (1.2.8)
is responsible for the superlattice reflections. It can be expressed through amplitudes of
concentration waves if one substitutes the representation (1.1.10) in eq. (1.2.5):
Aint(q) =fint ~ e-i'h' ~ 7~(k)uo(p, k) ~ e'~kR e -iqR

p a,k R
=fint E e-iqhP E 7a(k )Oa(p' k) E e-i(q-2'~k)R" (1.2.10)

p a,k R
Since
E e-i(q-2nk)g= q= 2rr(H + k
otherwiseif (1.2.11)
an important conclusion follows from (1.2.10) that each concentration wave (a, k) generates
its own set of superlattice reflections in points H + k of the reciprocal lattice, each two
superlattice reflections being separated by a fundamental reciprocal lattice vector H.
Therefore, if the position of a superlattice diffraction spot within the reciprocal lattice of
an ordered phase is known, the wave vector, k, of the concentration wave generating this spot
can be easily found. The vector k is merely equal to the distance from the superlattice spot
to the nearest fundamental spot.
It follows from eqs (1.2.8), (1.2.10) and (1.2.11) that amplitudes of the reflections generated
by the concentration waves with a wave vector k are
A(q) = (Aint(q))¢=2n(H+k)-----Nof i n t ~ e -~2n(H+k~p ~

p=l a=l
7a(k)oa(p,k ). (1.2.12)
Equation (1.2.12) reveals the essential fact that the amplitude of the superlattice reflection
in the point H + k of the reciprocal lattice is always proportional to the amplitudes of
concentration waves with the wave vector, k. It should be pointed out that the refinement
of eq. (1.2.12) by the inclusion of the host atom displacements, u(R), does not alter this
conclusion; it merely provides some additional contribution to the amplitudes of the
superlattice reflections rather than giving any shift of their location in the reciprocal lattice.
The contribution is caused by scattering from the periodic modulation of host lattice spacings
produced by ordered distribution of interstitial atoms.
Therefore, we arrive at the conclusion that the spectrum of concentration waves generating
the ordered phase is dictated by the diffraction pattern of the phase:
the wave vector of each concentration wave is determined by coordinates of the associated
superlattice spot within the first Brillouin zone of the host lattice built around the nearest
fundamental spot.
Correspondence between concentration waves and diffraction patterns proves to be

especially useful in complex structures where a host lattice unit cell is a small component of
the multiatomic unit cell of the structure. It is very difficult then to single out the host lattice
within the frame of the entire structure. The difficulties especially increase in the usual cases
where the host lattice is strongly distorted because of host atom displacements, and where
part of the host lattice sites are occupied by regularly spaced vacancies. The solution of the
problem requires considerable experience and good three dimensional vision. However, if the
geometric analysis is carried out within the reciprocal lattice, the procedure of determining
the host lattice becomes much simpler.
As a rule, fundamental diffraction spots have much stronger intensities than superlattice
spots. Apart from this, heterogeneous displacements and structural vacancies affect the
diffraction spot intensities but do not change their positions, i.e. do not affect the reciprocal
lattice geometry. These circumstances simplify the determination of the host lattice since its
reciprocal lattice is a Bravais lattice formed by fundamental diffraction spots. Knowing the
reciprocal lattice corresponding to the host lattice, one can readily determine the host lattice
itself.
As an example, the diffraction pattern of the spinel structure displays the strong spots being
fundamental reciprocal lattice points. They form the reciprocal lattice which may be
interpreted as the reciprocal lattice corresponding to the fcc host lattice whose crystal lattice
parameter, a, is one half the spinel crystal lattice parameter, asp. If the usual indices of
reciprocal lattice points of a fcc crystal are adopted, the coordinates of the superlattice
diffraction spots are {100} and {½1 ½}. Therefore, proceeding from the diffraction pattern
geometry alone, one may conclude that the spinel structure is formed by ordering along the
fcc host lattice, the ordering being generated by concentration waves with wave vectors
{kl} = {100} and {k2} = {½½½}.
2. STABILITY OF STOICHIOMETRIC COMPOUNDS

2. I. Concentration Wave Representation of the Configurational Energy of a
Chemical Compound
In Section 1.1 some kinematic properties of completely ordered atomic distributions
describing the structure of a stoichiometric compound were considered. These kinematic
properties, however, are not sufficient to predict the atomic structure of the compound. To
do it, one should introduce additional energy concepts which help to select the most stable
structures from the variety of all possible atomic distributions. The most stable structure must
have the minimum binding energy, the configurational energy per ordering atom. Here the
internal energy rather than free energy is considered because we discuss the particular case
of the structures being completely ordered up to the melting temperature. The latter condition
is realized if the typical energy of ordering substantially exceeds the heat energy ks Tm where
ks is Boltzmann's constant and Tm is the melting temperature. Any analysis of the structure
stability must begin with the construction of a general equation for the configurational energy
of an arbitrary atomic distribution. To construct such an equation, we will make the following
assumptions:
(i) interatomic interaction is pairwise;
(ii) the centres of all atoms can be associated with the sites and interstices of a Bravais
host lattice;
(iii) static atomic displacements from crystal lattice sites are ignored.
The latter assumption is not, however, necessary because the contribution of static
displacements into the atomic interaction energy is reduced to the renormalization of the
pairwise interaction energies and thus does not make the calculations more complicated. This
conclusion directly follows from the strain-induced interaction theory developed by Kha-
chaturyan which is valid within the framework of microscopic linear elasticity.(6'8)
We will consider below an interstitial system, though the conclusions are equally valid in
the more complex cases. The pairwise interaction in the Ising model results in the following
equation for the configurational energy: (1'3)
1
E=~ ~, Wpq(R-R')n(p,R)n(q,R') (2.1.1)
p,q R,R"
where the summation is carried out over all interstices {p, R} and {q, R'} of the host Bravais
lattice, Wpq(R - R') is the interaction energy of two interstitial atoms located in the interstices
(p, R) and (q, R'), and n(p, R) occupation number for the (p, R) interstice equal to either
one or zero.
Equation (2.1.1) may be simplified if we choose the eigenfunctions
~k (P, R ) = v~(p, k) exp(i2~kR ) (2.1.2)
of the matrix Wpq(R - R ' ) meeting the equation
~ Wpq(R -- R')~p~k(q, R') = 2,(k)~p~k(p, R) (2.1.3)

q=l R'
where 2~(k) is the eigenvalue of the matrix Wpq(R - R ' ) . Substituting (2.1.2) into (2.1.3) we
arrive at the equation for "polarization vectors" vo(p, k):
Vpq(k)o~(q,k) = 2o(k )v~(p, k) (2.1.4)
q=l
where
Vpq(k) = ~ Wpq ( e ) exp ( - i 2nkR ) (2.1.5)
R
is the Fourier transform of the matrix Wpq(R) and the "polarization vector" o~(p, k) is the
eigenvector of the matrix Vpq(k).
The matrix Vpq(k) is Hermitian, i.e. the relations
Vpq(k )* = Vpq(-k ) (2.1.6)
hold for it. To prove eq. (2.1.6), we shall use in the definition (2.1.5) of V*p(k) the equality
Wqp(R ) = Wpq(- R ) (2.1.7)
which follows from the obvious physical reason that the interaction energy of two atoms in
the positions (q, R) and (p, O) is not affected by their interchange. Indeed, utilization of eq.
(2.1.7) and change of variables, R ~ - R ' , result in the following chain of equalities:
V*(k ) = ~ Wq,(R) e a"kR = ~ Wpq(-R) e i2nkR

R R
~-"2 Wpq(R') e -i2nkR' : Vpq(k ). (2.1.8)

R'
The chain of equalities in (2.1.8) proves the Hermitian conditions (2.1.6).

Since eq. (2.1.4) is a set of homogeneous linear equations in unknown components
(o, (1, k ), o~(2, k) . . . . . u~(v, k )) of the generalized vector, a nonzero solution is obtained only
in the case when the determinant of the set (2.1.4) vanishes, i.e. when det II Vpq(k ) - 260q I] = 0
or
v.(k)-,~ v,2(k) ... v~v(k)
v * (k ) v2~(k ) - ;~ . . . v 2 v ( k )
= 0. (2.1.9)
v*v(k ) v*~(k ) vw(k ) - ,~
In the determinant (2.1.9) the Hermitian conditions (2.1.6) are utilized. One may readily
see that eq. (2.1.9) is an equation of degree v in 2. Because the matrix Vpq(k) is Hermitian,
eq. (2.1.9) has v real roots:
,~,(k), ,~2(k),... ,~(k),... ,L(k)
which form v branches of the spectrum of the matrix, Vpq(k ). Each eigenvalue 2~(k ) produces
its eigenvector, u,(p, k) which can be found from eq. (2.1.4). Since the concentration waves
q~,k(P, R) are defined as eigenfunctions of the Hermitian matrix Wpq(e -- e ') [see eq. (2.1.3)],
they form a complete orthonormal set and thus satisfy eqs (1.1.8).
Let us make a transition from the occupation number representation of an ordered state
determined by the set {n(p, R)} to a normal concentration wave representation determined
by the set of amplitudes, {?,(k)}. In other words, we shall make a transition to the diagonal
representation of the matrix Wpq(R - - e ' ) . Such a transition is convenient because the total
configurational energy (2.1.1) then becomes the sum of contributions of each concentration
wave, This result may be obtained if one substitutes the function (1.1.10) into (2.1.1) and uses
the relations (2.1.3) and (1.1.8). Then
E = ½N0 ~ 2~(k) I y~(k) 12 (2.1.10)

o,k
where the summation is carried out over all waves {a, k}. It follows from eq. (2.1.10) that
the configurational energy is a diagonal quadratic form of the amplitudes {?~(k )}. Therefore,
the transition from eq. (2.1.1) to (2.1.10) is in fact the diagonalization of the quadratic of
the variables {n(p, R)}.
2.2. The Maximal Amplitude Principle and Dominant Waves

The most stable superstructure should have the lowest configurational interaction energy
between interstitial atoms per interstitial atom (the lowest binding energy). The binding
energy which is also the chemical potential of interstitial atoms can be found from eq. (2.1.10):
E l (k)l 2
= = - - (2.2.1)
gb Nint 2 ~,k c
where
p=v gila t
c=yc,= ,
p=l NO
Nint being the total number of interstitial atoms.

Let us introduce the function
g,(k) = - - (2.2.2)
C
in eq. (2.2.1). The result is

1
eb = 2 ~ 2~(k )g,(k ). (2.2.3)
a,k
Substituting the left-hand side of eq. (1.1.15) for c in (2.2.2) we have
17,(k) 12 (2.2.4)
go(k) - I o.(k')12
where the summation is taken over all concentration waves {a',k'}. The function go(k)
defined by eq. (2.2.4) satisfies the equation
go(k) = 1. (2.2.5)
a,k
If follows from eqs (2.2.3), (2.2.4) and (2.2.5) that g~(k) is a weighting function which
describes the partial contribution of each eigenvalue 2o(k) [of each concentration wave (a, k )]
to the binding energy eb.
It should be mentioned that the eigenvalues 2~(k) of the matrix Wpq(R - R ' ) are always
degenerated with respect to the concentration wave {a, kjs } belonging to the same star of the
wave vectors {kjs } where Js denotes the wave vectors of the s-th star (a star is a set of wave
vectors kjs that may be obtained from one of them by applying to it all operations of the
symmetry group of the disordered solution; the vectors kj~ differing from each other by a
fundamental reciprocal lattice vector H being assumed to be identical). This degeneration is

caused by the host lattice symmetry. Bearing in mind the degeneration within each star, one
can rewrite eq. (2.2.3) using the summation over the stars instead of the summation over the
wave vectors:
1
Sb = ~ ~ Z,,sG,s (2.2.6)
a,a
where 2,,, is a value assumed by the eigenvalue ),~(kj,) for any wave vector, hi, of the star s,
G~s, = ~g,(kj,)j, = -cl ~. t ?,(kj,) 12 (2.2.7)
is the new weighting function related to the contribution of each star rather than each wave
vector. The weighting function Q,s by the definitions (2.2.4) and (2.2.5) also meets the
normalization conditions
G~., = 1 (2.2.8)
¢7,S
where the summation is carried out over all set of (a, s).
It follows from (2.2.6) and (2.2.8) that the binding energy sb reaches its minimum value
when the dominant contribution to (2.2.6) is made by the smallest eigenvalue 2,0~0, of the
matrix Vpq(k) (,~0s0 = min 2~(k)). The latter occurs when the partial contribution, G~0~0of the
minimum eigenvalue, 2,0~0 is the maximum possible value. According to the definition (2.2.7),
this requirement is reduced to the following:
the crystal structure of a compound is stable if the sum of squared amplitudes,
[ ?~o(kJs0)12 (2.2.9)
related to the minimum eigenvalue 2~o,o assumes the maximum possible value consistent
with the relevant composition c.
For brevity, let this condition be named the maximal amplitude principle, and the
concentration waves {ao, kjso}, related to the minimum eigenvalue, 2~o~o,be named dominant
waves.
It should be emphasized that in eq. (1.1.10) for n(p, R) the zeroth term
C
71(0)o,(p, 0) = 7~v ol(P, 0) (2.2.10)
v
is always present. In eq. (2.2.10)

vl(p, O)= 1 (1, 1, 1,,..., 1) (2.2.11)
7
is the v-component eigenvector of the matrix
v,,(o) v,2(0) v,2(o)...v,2(o)~

V,~(O) =
T/T! /
v,2(o) v,2(o) v,2(o)...v,(o)3
(2.2.12)
consisting of v rows and v columns• The corresponding eigenvalue is

21(0) = ~'rll(0) - (v - l) V,2(0). (2.2.13)
If the function, n(p, R), includes the zeroth term only, i.e.
f c/v when p = l
•c/v
...............
when p = 2
no(p, R) = ~x/ v o l ( P ' 0) = (2.2.14)
L.c/v when p=v
it describes the completely disordered state in which all interstices are filled by interstitial
atoms with equal probabilities, c/v. The term (2.2.10) is, therefore, responsible for the
conservation of the total number of interstitial atoms. As for the other concentration waves,
they modulate the disordered distribution of interstitial atoms and thus, are responsible for
the formation of an ordered phase (superstructure)•
Since the sum of squared amplitudes of all concentration waves entering eq. (1.1.10) is the
conserving value depending only on the total concentration c [see eq. (1.1.15)] an increase
of modulus of the dominant wave amplitudes can only be obtained by decreasing modulii
of the remaining amplitudes• The most favorable situation arises when amplitudes of all
waves other than the dominant ones and, of course, the zeroth wave ¢pl(p,R)= o~(p,O)
responsible for conservation of the number of interstitials are equal to zero. This case is
named favorable because, as it can be seen from eq. (2•2•6) and (2.2.8), it provides the
minimum value of the energy/3b. Such a favorable distribution may be rewritten in the form
C
ndom(p, R) = ~ vl(p, 0) + ~ ?~o(kj~o)o~o(p,kjso)eiE~kJs0R (2.2•16)
x/v Js 0
or, with due regard for (2.2•14),
ndom(p, R) = c + ~ ?~0(kjs0)v~0(p' kj~o) ea,%oR' (2.2.17)

Y J~o
The summation rule (1.1.15) for a structure described by the distribution (2.2.16) may be
presented as
c_: + Z I Yoo(k,~o) I ~ - c. (2.2.18)

Y js o
It follows from (2.2.18) that the sum of squared moduli of the dominant wave amplitudes
is
E I7%(kjso)12=-c(1-~). (2.2.19)
L0
Therefore, the sum of squared moduli of the dominant wave amplitudes generating a
favorable structure is the value depending only on the stoichiometric composition. A question
arises, whether any ordered atomic structure may be represented in the form (2.2.17), in terms
of the dominant waves alone.
Unfortunately, the answer is negative. The reason is the kinematic constraints imposed on
the function n(p, R) (see Section 1.1): eq. (2.2.17) does not always fit the condition for the
function n(p, R) to be equal either to zero or unity. Representation of the function n(p, R)
only ia terms of dominant waves belonging to the same star So and "polarization" ~0, i.e.
in terms of functions inducing an irreducible representation of the space group, is possible
only for the very specific cases corresponding to the most stable phases. These cases will be
considered below. Although these constraints significantly complicate the mathematic
analysis, they give us also a significant advantage, in that they enable us to reduce
dramatically the number of the most stable (favorable) structures under consideration
because these structures should be described by eq. (2.2.17). Reformulating this in terms of
the space group representation theory widely used in the phenomenological theory of
second-order transitions by Landau ~9) and Lifshitz,(1°) we can see from eq. (2.2.17) that the
most stable superstructures are generated by the only irreducible representation of the space
group of the host lattice (by definition, concentration waves, {a0, kj,0} in eq. (2.2.17) induce
one irreducible representation). Therefore, the maximal amplitude principle is equivalent to
the requirement for the structure to be generated by the only irreducible representation.
It is noteworthy that the same conclusion follows from the phenomenological second-order
transformation theory. According to Landau, ~9)the structure of an ordered phase arising in
the second-order transformation is also determined by the only irreducible representation of
the disordered phase space group. Static waves inducing this irreducible representation form
so-called "soft modes". In this respect the results of both theories coincide regardless of the
diametrically opposite assumptions in their foundation. While the Landau theory proceeds
from the assumption of infinitesimal amplitudes of concentration waves, the present theory,
on the contrary, is valid for completely ordered structures, the amplitudes of concentration
waves for which we assume the maximum possible values.
2.3. Stability of Layer Structures

As mentioned above, the function n (p, R) in the form (2.2.17) does not necessarily assume
only two values, either zero or unity. This can be seen from the very fact that a combination
of any two wave vectors entering (2.2.17) is equal again to one of the wave vectors in (2.2.17)
only for very specific particular cases (see the necessary conditions formulated in Section 1.2).
With all other cases (and they form the overwhelming majority) we have to introduce into
the function (2.2.17) additional nondominant waves {a, k } to satisfy the criterion for the sum
of wave vectors. This is, however, disadvantageous from the viewpoint of the maximal
amplitude principle, because to meet this principle we should analyze the superstructures
generated by the minimum number of additional nondominant waves. The latter follows from
the summation rule (1.1.15), according to which the reluctant introduction of additional
nondominant waves results in the decrease of the dominant wave amplitudes and, therefore,
the decrease of the partial fraction
XI I
G,0s° = J,o
E I I=
,,k
of the minimum eigenvalue 2,0,0 in the sum (2.2.6). Thus, if not all concentration waves in
n(p, R) are dominant, we must, at least, select the dominant waves so that the number of
complementary nondominant waves would be minimal and their amplitudes would assume
minimal possible values.
As was shown in Section 1.2, the sum of two wave vectors in (1.1.10) must also be equal
to the wave vector in that equation (1.1.10). To insure this, we have to add to the dominant
waves the group of complementary nondominant waves whose wave vectors are arbitrary
sums of wave vectors of the dominant waves. It follows from the foregoing that the wave
vectors of all the waves generating the distribution (1.1.10) are described by the periodic net
of the superlattice points inscribed into the reciprocal lattice of the host crystal, the unit
translations of this net being the wave vectors of the dominant waves.
Therefore, if the wave vectors of the dominant waves in (1.1.10) are not colinear, their sums
generate two- and three-dimensional nets of superlattice points in the host crystal reciprocal
lattice. If, however, only the conjugated dominant waves, (a0, k0) and (a0, - k 0 ) with the
colinear vectors k0 and - k 0 , are included, one may readily see that their sums generate a
one-dimensional set of equidistant points situated along straight lines. In the latter case we,
of course, have a smaller number of wave vectors associated with the nondominant waves
than in the cases of two- and three-dimensional nets and, thus, in compliance with the
maximal amplitude principle come to the more stable structure. This seems to be the reason
that "one-dimensional structures" are so widespread. As will be shown below they are layer
structures described by alternation of occupied and vacant parallel crystal lattice planes.
Let us consider in more detail the "one-dimensional case" when a superstructure is
generated by two conjugated colinear dominant waves, (a0, k0) and (a0, - k 0 ) . In this case
eq. (2.2.17) may be rewritten as
1
* k o*,0(P, k0) e -~2~k0n
ndom(p, R ) = - c + 70o(ko)v,o(p, ko) e '2"k°R+ • *0(0) (2.3.1)
v
The simplest way to determine the nondominant waves which we have to add to eq. (2.3.1)
is to make use of eq. (1.1.12), i.e. to raise eq. (2.3.1) to the integer power sl:
[ndom(P, R)] s~ = + y,o(ko)o,o(p, ko) e '2~k°" + ?*o(ko)o,o(p, ko)* e -i2~k°R (2.3.2)
where Sl is the minimum integer for which the equation
slk o = H (2.3.3)
holds, and H is any reciprocal vector of the host lattice. The integer s~ will be referred to as
multiplicity of the vector k0.
One may easily see that the right hand side of eq. (2.3.2) is a polynomial where the new
exponentials of the kind of exp(_+ i2nkosR) arise (s = 0, 1, 2 . . . . . S1 - 1). These exponentials
describe new concentration waves with wave vectors
ks = sko (2.3.4)
where s = 0, 1, 2 . . . . . Sl - 1.
Expanding the polynomial (2.3.2) into a series of the eigenfunctions v,(p, k) e ':"kR, the new
(nondominant) concentration waves which are not represented in (2.3.1) may be found. To
determine the full function n(p, R ) including both, dominant and nondominant waves, we
must supplement the function ndom(P, R) with these additional nondominant waves, otherwise
the identity (1.1.12) cannot be provided.
The function n(p, R ) which was derived from the function (2.3.1) by the above method
can be presented in the form (1.1.1):
S=sI--I
n(p, R ) = ~ a(p, sko)e '2~s*°R (2.3.5)
s=0
CHARACTERIZATION OF C E R A M I C CRYSTALS 17
where
Cr=V
a(p, sko) = ~ y~(sk )vo(p, sko). (2.3.6)

a=l
It follows from the definition (1.1.3) that

a(p, k + H ) = a(p, k ) (2.3.7)
since, by the definition of a reciprocal lattice vector,
e x p ( - i 2 n H R ) = 1. (2.3.8)
Using the identity (2.3.7) and the definition (2.3.3) of the multiplicity number s~, we have
a(p, (s~ - s)ko) = a(p, H - sko) = a(p, - s k o )
or
a(p, (s, - s ) k o ) = a(p, - sko). (2.3.9)

Taking into account (1.1.2), eq. (2.3.9) may be rearranged:
a(p, (sl -- s)ko) = a*(p, sko). (2.3.10)
Since all the wave vectors (2.3.5) are colinear, the distribution functions (2.3.5) describe layer
superstructures with alternating planes of filled and vacant interstices normal to the vector
k0.
Recall again that the relevant layer superstructures are more stable than the nonlayer ones
because they involve a smaller number of additional nondominant waves and are, thus,
preferable from the viewpoint of the maximal amplitude principle. This consideration seems
to be the reason why the layer structures are so widespread.
The rule requiring the formation of layer superstructures is violated comparatively rarely
for the particular cases when the minima of 2o(k) fall at such vectors of the star {k0 } which,
when combined, give either a vector of the same star or a fundamental reciprocal lattice
vector, H.
2.4. The M o s t Stable Layer Structures with Fixed Stoichiornetry

Let us discuss the energetically most favorable specific cases when the distribution function
(2.3.5) can include only the dominant waves (tr0, k0) and (tr0' -k0). The function n(p, R ) then
is
c
n(p, R ) = - + a(p, ko) e a~k°R + a*(p, k0) e -'~k°R (2.4.1)
v
where
a(p, ko) = y~o(ko)o~o(p, ko). (2.4.2)
The function n(p, R ) in (2.4.1) can assume only two values, either unity or zero and,
therefore, describe the distribution function only in three particular cases.
This is the case st = 2, when, according to eq. (2.3.3)
k0 = ½H. (2.4.3)
With k0 = 1 H the atomic distribution of each "filled" sublattice of interstices is described by
J P M . S . 29/ -2 B
one of two functions

n(p, R) = ½+_1 exp(i2nkoR ) = ½+_½exp(inHR ) (2.4.4)
where p denotes the "filled" sublattice.
Since H R is an integer by definition, exp(inHg) is either + 1 or - 1 and the function
n(p, R), eq. (2.4.4), is either 0 or 1 on all interstices {p, R} of the p-th sublattice. Equation
(2.4.4) includes only one concentration wave instead of two waves with k0 and - k0 since for
k0 = 1 H, k0 = - k0 + H, i.e. k0 = - k0 to within the reciprocal lattice vector H. The distribu-
tion (2.4.4) corresponds to the occupation numbers cp = ½.
The other favorable case when the distribution n(p, R) is generated by dominant waves
alone and thus has the form (2.4.1) arises at sl = 3. Then
,o=iH=IH
sl 3 "
In this case 2k0 = - k 0 + H ; i.e. 2k0 = - k 0 to within the reciprocal lattice vector H. In other
words, the situation is favorable because any sum composed by the vectors k0 and - k o is
again equal to one of these vectors or to zero to within the reciprocal lattice vector H.
For k0 = ] H the atomic distribution in a "filled" p-th sublattice of interstices is described
by either
1 1
n(p, R) = -~ + ~ [exp(i2rckoR ) + e x p ( - i27~koR)]
1 2 1 2 2re
= ~ + ~ cos 27rkoR = ~ + ~ cos ~ HR. (2.4.5)
or
2 2 2 2 2re
n(p, R) = ~ - ~ cos 21rkoR = ~ - ~ cos - ~ HR. (2.4.6)
The functions (2.4.5) and (2.4.6) also assume only two values, 0 and 1, since H R is, by
definition, an integer at any site R. The function (2.4.5) describes the layer structure in which
every third plane normal to the vector H and drawn in the p-th sublattice is occupied by
interstitial atoms. Therefore, Cp = ½.
The function (2.4.6) describes the antiisomorphic structure in which every third plane
normal to the vector H is vacant and all others are occupied by interstitial atoms. For this
structure Cp = 3.
Finally, a third type of the layer structure generated only by dominant waves occurs in the
case sl = 4. Then
ko = ¼H (2.4.7)
and the distribution (2.4.1) assuming only two values, 0 and 1, has the form
n(p, R) =
1 + 1 4 i e,2,~koR --b--~e-
1 + i ,2,~koR
1 1
= ~ + ~ [cos 27rkoR + sin 2rtk0R ]. (2.4.8)
Substituting (2.4.7) into (2.4.8), we have
n(p,R)=~+~ cos~HR +sin HR . (2.4.9)
Since the scalar product HR is an integer, eq. (2.4.9) assumes either 0 or 1 on the sites of
the p-th sublattice, {p, R}. For the structure (2.4.9) % = 1.
It is noteworthy that the distribution (2.4.8) is the example mentioned in the footnote in
page 6. The specific choice of the wave vector (2.4.7) and amplitudes,
1-i 1+i
a(p'k°)= 4 and a ( p , - k o ) = a * ( p , ko)=--~--,
results in vanishing of the amplitude of the nondominant wave exp(i2rt2koR) with the wave
vector 2k 0 which arises in the right-hand side of eq. (1.1.10).
At first sight we may expect eqs (2.4.4), (2.4.5) and (2.4.9) to be valid at any vector H and
host Bravais lattice. This, however, is not the case. Since the distributions (2.4.4), (2.4.5) and
(2.4.9) are generated by the dominant waves (tr0, k0) and (a0, - k 0 ) alone, they must be also
described by the distribution (2.3.1). Equation (2.3.1) is, however, reduced to eqs (2.4.4),
(2.4.5) and (2.4.9) only in the case when specific, quite rigid relations between components
of the eigenvector Ooo(P,k0) = [oo0(1, k0), o~0(2, ko) . . . . . O~o(V,k0)] hold. This, in turn, takes
place only for some very specific reciprocal lattice vectors H in (2.4.4), (2.4.5) and (2.4.9).
Therefore, we have one more, very rigid constraint imposed on the vectors, H, entering eqs
(2.4.4), (2.4.5) and (2.4.9) and thus on the type of possible stable superstructures.
In addition to the above general cases described by the distributions (2.4.4), (2.4.5) and
(2.4.9), there are particular cases of layer structures the realization of which is possible
because of the specific reciprocal lattice geometry of the host crystal. In these particular cases
all the wave vectors k, = sko where s = 1. . . . . s~ - 1 prove to belong to the same star rather
than to different ones and, consequently, may be related to the dominant waves.*
One of these structures is generated in the fcc host lattice by the dominant wave whose
wave vector is 1/5 of the fundamental reciprocal lattice vector, (420). This is the case when
sl = 5. The function (2.3.5) then is
1
n(p, R) = -~ + -~ exp(i2rtskoR) (2.4.10a)
S=I
where
ko = -~(420) = (4 ~ 0). (2.4.10b)
As will be seen, all the vectors k~ = sko in (2.4.10a), to within a fundamental reciprocal
lattice vector, belong to the same star {4 ~ 0} and, therefore, may be related to the dominant
waves. Indeed, equations
lk 0 = l x ( 4 - ~ 0 ) =
2ko = 2 x (~2 O) = = (~ ~ O) + (200) --, ( ~ O)
3ko = 3 x (4~ O) = (~ 6 0) = (2 ~ 0) + (220) -, (2 ~ 0)
4k0 = 4 x ( 4 2 O) = (9 ~ 0) = (4 ~ 0) + (420) -, (4 g 0)
*As was mentionedabove, a star is a set of wave vectors kj that can be obtained from one of them by applying
to it all operations of the symmetrygroup of the disordered solution, the vectors kj differingfrom each other by
a fundamental reciprocal lattice vector being assumed to be identical.
hold within the fundamental reciprocal lattice vectors of the fcc host crystal, (000), (200),
(220) and (420), respectively. In this case the function (2.4.10a) can be rewritten as
1 s--4 /.2re \
n(p, R) = ~ s~oeXp ~l-~ sU(42o)R) . (2.4.11)
The distribution (2.4.11) assumes only two values, 0 and 1, and describes the layer
structure.
x [][][][] × [] [ ] [ ] [] × • . . . (2.4.12)
of filled and vacant planes (420) where x is a filled plane and [] is a vacant plane. The
fraction of filled planes is cp = 1/5.
A similar structure is generated in the fcc host lattice by a dominant wave with a wave
vector
ko = + Ht35 = (T 3 ~) (2.4.13)
As with the vector (2.4.10b), all multiples of the vector k0, ks = sko, belong to the same
star {~35
77}.
We have the relations
T3 T3
3ko = (7~ 97 ~ ) = (73~7 7I ) + (022)--,(~- -~I 7)

4k ° = , ¢7_122%_
7 7 7 ~ - ( 7 35T
7 7 ) + ( T 1 3 ) ~ 7 7,35T~
7)
5k0 = , 7t3-_15
7 25~
7 , = ( q 5q T~ 3) + ( 0 2 4 ) ~ ( T q5~~) 3
6ko = , 7(~ 18
7 30~
7 , = ( 7 71"~5"
7 ) + ( i 3 5 ) ~ ( 7 7 ~1~--
)
which hold to within the fundamental reciprocal lattice vectors, ( i l 1), (022), (T13), (024) and
(i35) of the fcc host crystal, respectively. In this case the distribution (2.3.5) reads
1 6 ~
n(p, R ) = - ~ e a"k°'R = _1 ei(2n/7)sH(135)R" (2.4.14)
7 s=0 7 s=0
The function (2.4.14) is equal to either 0 or 1 and describes the layer superstructure formed
due to the alternation of the filled and vacant planes (135) drawn in the p-th fcc sublattice
of the host crystal in the sequence
x Dill-q[] []1--] x I--] I-] I--] I--] [] [] x . . . (2.4.15)
The fraction of filled planes is cp = 1/7.
To summarize this section, notice that all the above considered atomic distributions
correspond to the fixed fraction ce of planes occupied by interstitial atoms [the fraction G
is described by the zeroth term of the distributions (2.4.4), (2.4.5), (2.4.9), (2.4.11) and
(2.4.14)]. Consequently, the corresponding chemical compounds must also feature fixed
stoichiometry. These compounds are composed of atoms having fixed integer valencies.
2.5. The Nature of Homologous Series of Chemical Compounds

In Section 2.4 the concentration wave approach and, especially, the maximal amplitude
principle were applied to the theoretical determination of stable structures composed of atoms
with fixed valencies. These structures are generated only by dominant concentration waves.
It was shown there that the wave vectors of the dominant wave of such structures cannot
assume an arbitrary value. The wave vectors should be equal to 1/2, 1/3 or 1/4 of a
fundamental reciprocal lattice vector, H, of the host crystal. A question then arises concerning
what would happen if the minimum eigenvalue ;t,o~o, which determines the choice of the
dominant waves, is realized with a wave vector, k0, which does not satisfy the above
1 1 1
constraint, namely, that it must not be equal to ~H, ~H or ~H. As shown above, in this case
the dominant wave should inevitably be supplemented with nondominant waves whose wave
vectors, ks = sko, are multiples of the wave vector ko(s = 2, 3. . . . , Sl - 2).
In trying to answer this question we will arrive at the surprizing conclusion that in this case,
specific phase states forming the homologous series of chemical compounds may exist. These
compounds named the Magneli phases have been observed in many transitional metal
oxides.{~l-16)
Since such structures are generated by both the dominant and nondominant waves, they
are less stable than the structures discussed in Section 2.4, because the latter ones are
generated only by dominant waves. The formation of the structures with the arbitrary wave
vector k0 results from the constraint imposed on the stoichiometric composition by the
variable valencies of atoms forming the crystal rather than from minimizing the
configurational energy (2.2.6). Incidentally, this seems to be the reason why the homologous
series are not wide-spread structures. However, even in the unfavorable case of an arbitrary
k0 the maximal amplitude principle can be employed to determine the structure of the
homologous phase.
The maximal amplitude principle requires that the sum of the squared moduli of the
dominant wave amplitudes,
I I (2.5.1)
J~
be their maximum value. Since we discuss layer structures, only the two dominant waves,
(a0, k0) and (a0, -k0) are taken into account. In this case eq. (2.5.1) reads
l o(kj o) l 2 = 21 T 0(k0) 12 (2.5.2)

Js o
because y~0(-k0) = y*0(k0).

To determine the stable structure of a layer phase we should:
(i) find the sequence of occupied and vacant parallel planes drawn within the interstice
sublattices of the host lattice framework;
(ii) find the indices of the plane generating this sequence;
(iii) find the mutual positioning of the layer distributions of interstitial atoms in the
various sublattices.
The final refinement of the structure also requires the calculation of small displacements
of host atoms resulting from ordering of interstitial atoms.
Let us show how the first step, the determination of the sequence of occupied and vacant
planes, can be made by applying the maximal amplitude principle. The minimization of the
binding energy (2.2.1) is possible due to the choice of the optimal sequence of occupied and
vacant planes in the layer superstructure which would provide the maximum amplitudes of
the dominant waves on the expenses of minimizing or vanishing of the amplitudes of
nondominant waves.
It should be noted that the concentration wave (a, k0) at ~ # a o, in contrast to the
wave (tro, ko), is a nondominant wave since it is associated with the eigenvalue
2~(ko) > 2oo(k0)= 2oo~o. This means that a decrease of the amplitude y,(k0) of the non-
dominant wave (a, ko) should result in an increase of squared moduli of the amplitudes of
dominant waves 2 ] )'oQko) ] 2. In the most favorable cases the amplitude 7o(k0) (tr # tr0) must
vanish. This is exactly the case which will be considered.
The condition yo(ko)= 0 at tr # ~o sharply reduces the choice of possible vectors ko of the
dominant wave since the vector ko, for which superstructure can be obtained without
nondominant waves, (tr, k0) (a #tro), should be quite special. If Y~(k0) = 0 at tr # tro, eq.
(2.3.6) is simplified:
a(p, k0) = V,0(ko) x O~o(p,ko). (2.5.3)
It follows from eq. (2.5.3) that
2 [a(p, ko) l 2 = 2 [ ~o0(ko) 121 O.o(p, k0) l =, (2.5.4)
i.e. the values 2 [ a(p, k0) [ 2 and 2 [ V,o(ko) [ 2 are proportional to each other. This means that
the maximal amplitude principle can equally be applied for both, amplitude a(p, ko) and
~0(k0).
Now we formulate the structure determination procedure for a layer superstructure
providing the maximum possible value l a(p, k0) l 2 and thus meeting the maximal amplitude
principle. In compliance with eq. (2.3.3), the vector H is the minimal magnitude vector of
the reciprocal lattice which can be produced by multiplying the vector k0 by an integer. The
vector H is not necessarily equal to the shortest reciprocal lattice vector H0 lying along the
same direction. It may be longer than H0 by an integer factor So, i.e.
H = Hos o. (2.5.5)
This situation is illustrated by the following simple example. Let the vector k o in the fcc
host crystal be determined by the point (~ 2 z)
5 and be directed along the [111] axis. One can
readily see that the smallest integer which can produce, according to eq. (2.3.3), a
fundamental reciprocal lattice vector is s~ = 5. Indeed,
S, ko = 5(222-)=(222)5
where (222) are the indices of the reciprocal lattide vector, H(=2). The shortest reciprocal
lattice vector directed along [111] has, however, indices (111) rather than (222). Therefore,
Ho = H{nl), H = H(=2) and So = 2.
It follows from (2.5.5) that
n Sono
k0 . . . . . (2.5.6)
S1 S1
n(p,R)=
S=Sl-lfs°U°x~(~l° )
~ a ~p,s--~l ) e x p
s=o is noR . (2.5.7)
Equation (2.5.7) can be simplified if the analytical equation for the set of crystallographic
planes,
HoR = m, (2.5.8)
is used, where m = 0, +__1, _ 2 . . . . are the numbers of parallel planes normal to the vector
H0. Substituting (2.5.8) into (2.5.7) we have
n(p, R) = %(m) = ~ ap(s) exp i sm (2.5.9)

s=0
where %(m) is the probability to find an interstitial atom at one of the sites of the m-th plane
drawn in the p-th sublattice of the host crystal [rip(m) is equal to either zero or unity] and
ap(s) is the shorter notation for the amplitude
The index m in eq. (2.5.9) acts as the spatial coordinate. Describing the atomic distribution
n (p, R) in terms of the only descrete variable, m, proves to be possible because the initial eq.
(2.3.5) describes the layer superstructure, i.e. the one-dimensional superstructure where all
sites of a plane normal to H0 are either vacant or occupied.
Equation (2.5.9) leads to the conclusion:
np(m + s~) = np(m) (2.5.10)
which implies that the multiplicity s~ of the wave vector k0 of the dominant wave is also the
period of the layer structure generated by this wave. Consequently the translational motif of
the layer superstructure described by eq. (2.5.9) consists of Sl parallel planes associated with
the reciprocal lattice vector H0.
According to eqs (1.1.3), (2.5.6), (2.5.8) and (2.5.10), the amplitude ap(S) may be
represented as
1 s1-1 / 2ns0 "~
ap(S)=-~ ~ np(m)exp{-i sm]. (2.5.11)
°1 m=O \ S1
Let s~ planes forming the translational motif of the layer superstructure in the p-th
sublattice of interstices include m 0 planes completely occupied by interstitial atoms and
s~ - m0 completely vacant planes. The stoichiometric fraction of occupied interstices of the
p-th sublattice can be then written as
Cpst = ap(0) - ~ ' m°

--. (2.5.12)
St
Since, by definition, np(m) is either one (for occupied planes) or zero (for vacant planes),
the sum (2.5.11) is a mere sum of m0 exponentials,
exp(/ m)
taken over the numbers of occupied planes, m'. In other words,
where m' are the consecutive numbers of occupied planes within the motif consisting of Sl
planes in which %(m) is equal to 1 (i.e. %(m')= 1).
By definition, the amplitude of the dominant wave with the wave vector k 0 corresponds
to s = 1. Hence
ap(1) = sl--1~eXPm,( - i2~z s,

s° m'')" / (2.5.13)
Therefore the first step in the determination of a stable layer structure is reduced to the
determination of the consecutive numbers, m' of the m0 planes of the motif filled by interstitial
atoms. This can be made with the help of the maximal amplitude principle. To make the
modulus of the dominant wave amplitude (2.5.13) maximal for a specified number of filled
planes, m0, we must choose the consecutive numbers of filled planes, m' such that the modulus
of the sum in (2.5.13) is maximal. For this to be true the difference between the phases of
the exponentials,
exp ( - i 2 n S°m'~
S1 ,]
indexed by numbers, m ' , must be minimal.

The simplest method to determine the maximum of the amplitude (2.5.13) consists in
employing a graphical construction, the so-called clock diagram. This method is based on
the fact that each term in (2.5.13) may be represented graphically as a radius-vector of a unit
circle in a complex plane which make an angle of
q~(m') = 2re Som'

SI
with the real axis (here m' is the number of the filled plane which is associated with the radius).
The sum in (2.5.13) may thus be reproduced in the complex plane as a sum of m0 unit vectors
whose directions are determined by their angles q~(m'). One may easily see that the sum
increases as angles between the nearest unit vectors decreases. The latter, in fact, dictates the
choice of the filled plane numbers, m': the numbers m' should be chosen such that the
difference between the angles ~0(m') referred to the filled planes is minimal.
To illustrate how this principle works, let us consider first the case of So = 1. Equation
(2.5.13) is simplified at so = 1:
ap(1) = __1~ exp ( - - i 2~z m'~. (2.5.14)

SI m' SI /
The unit radius-vectors in the complex plane describing all exponentials,
e-i(2="#')(m = O, 1, 2 , . . . , s~ - 1) are displayed in Fig. l(a) for the case ofsl = 9. The number
near each radius-vector in that figure is the index number m of planes making up the
crystallographic motif comprising sl = 9 planes, and the angles made by these vectors with
the real axis are equal to the exponent phase,
2rt
q~(m ) = --~- m.
It follows from Fig. la that the smallest possible angle between the unit vectors is
2r~ 2re
Sl 9
This enables us to find the index numbers m' of the unit vectors associated with the filled
planes. It is easy to see that the magnitude of the vector sum of mo unit vectors reaches its
7 5
6 8 3 7
(a) (b)
FIG. 1. The clock diagram for determination of the sequence of alternative filled and vacant planes.
(a) Wave vector of the d o m i n a n t wave,
2n
k0 = - - H0, (sl -- 9, So = 1).
SI
(b) Wave vector o f the d o m i n a n t wave,
ko = 2nSo H0, (sl = 9, so = 5).

SI
maximum when we choose m0 nearest vectors in succession so that they make the smallest
angle with each other equal to
2n 2zt
sl 9
The maximum possible amplitude of the dominant wave ap(1) at a given value
st mo
Cp 2 - -
Sl
is then determined by eq. (2.5.14) where the summation over m' is carried out from 0 to
m 0 - 1:
m0
sin 7t - -
lm'='n°-' ( 27Z ) S,
ap(1)=~l ,~0'= exp --i--m'sl = r~ e-i(~/")("°-l)
s~ s i n -
sl
= e_i(r~/sl)(mo_l) sin nCp'S (2.5.15)

lz
s~ s i n -
st
(the result will be the same to within the phase multiplier if summation is taken from m to
m + m 0 - 1, i.e. if the origin is chosen at any m-th plane). The squared modulus of the
amplitude (2.5.15) is
[ap (1) 12 = sin2 rCCp' (2.5.16)
s2 sin2 rc
s1
The squared moduli of the remaining nondominant concentration waves are evaluated in a
similar way. They are
Iap (s) 12 = sin2 rtsc~'. (2.5.17)

s~ sin 2 ns
Sl
With s o > 1, each exponential in the sum (2.5.13) may also be related to the unit vector making
an angle
q~(m') = 2rtS° m '

Sl
with the real axis. The unit vectors describing all the exponentials,
exp(--i2~S°m~(m = O , 1,2 . . . . . s ~ - l )
\ s, /
are presented in Fig. l(b) for the particular case of s~ = 9 and So = 5.
As in Fig. l(a), the numbers drawn near the vectors are the index numbers, m, of s, = 9
planes, and the angles made by these vectors with the real axis are equal to the corresponding
phase,
2ns0 2n 5
~o(m)= s, m = ~ - - m .
It follows from Fig. 1(b) that, to within the numbering of unit vectors, their arrangement at
so = 5 remains the same as with So = 1. Therefore, like with So = 1, the maximum value of the
magnitude of the sum of mo unit vectors shown in Fig. l(b) is attained when we choose a
succession of rn0 nearest unit vectors making the angles of
2n 2re
q) --
s, 9
with each other. This signifies that the squared moduli of the amplitudes of the dominant
wave and nondominant waves are determined by the same eqs (2.5.16) and (2.5.17),
respectively.
For example if the fraction of occupied interstices of the p-th sublattice is
s, m 0 5
Cp - sl 9 '
i.e. 5 of 9 planes are completely occupied by interstitial atoms, the index numbers of five
nearest occupied planes in the case of So = 1 are, according to Fig. l(a), 0, 1, 2, 3, 4. The
corresponding sequence of occupied and vacant planes is then
...ix x x x xOO[O[~x x x x xOOFIOx... (2.5.18)

sI= 9
where x and [] are symbols designating occupied and vacant planes.

Figure 1(b) shows that in the case of So = 5 and m0 = 5 the numbers of the nearest occupied
planes are 0, 2, 4, 6, 8. The corresponding sequence of occupied and vacant planes is
...i--Ix ,x I--I x r-1 x ~ x IS] xj x F-I x I-1 x E3 x IZ] x . . . (2.5.19)

s I =9
st provide
Let us now raise the question, what values of the stoichiometric composition Cp
the maximum possible amplitudes of the dominant waves and, therefore, provide the most
stable compound, and what is the associated sequence of occupied and vacant planes?
To answer this question we should find the maximum value of the expression
tk(sl, c~t) = 2 sin2 nc~t (2.5.20)

s2 sin2 n
Sl
which, according to (2.5.16), is the squared modulus of sum of two dominant wave
amplitudes.
It follows from eq. (2.5.20) that the function q~(s1, Cpt) increases with a fixed Cp as the st
translational motif period sl decreases. The latter conclusion is illustrated by the monotonic
decrease of the function
(, sin ) v ,l
plotted in Fig. 2. Consequently, the following two statements are valid:
(i) Any aperiodic alternation of occupied and vacant planes (the case s] ~ o0) leads to
a lower value of 4~(s~, c~t) and is, thus, less stable than a periodic distribution (the
case of a finite s~) with the same composition Cp. St
(ii) A layer structure with a lower value of s~ has the larger value of 4)(s~, c; t) and is,
thus, more stable than a layer structure with a larger value of s~ and with the same
composition %. st
Therefore, a superstructure with the minimum possible period s~ consistent with the
fraction of occupied planes,
st m0
Cp ~ - - ~
Sl
has the maximum amplitude of the dominant wave. In the context of the definition (2.5.12)
this means that the value of cpst should always be represented as an irreducible fraction, mo/s~,
whose denominator is interpreted as the superstructure period, sl. Otherwise, if the period
of a layer structure is denominator, s~, of a reducible fraction, cp =mo/s~ where
f St t /
Q25
o.z
Q,'5
oj
, i , , ~ , b b i i , J , i i
¢# ¢~"
FIG. 2. Plot o f (s~ sin vs s~.

m6 = lmo, s~ = lsl, l is an integer, this structure would be less stable than the alternative layer
structure with the same value of cpt = mo/sl = m6/s~, but with a period s~ which is less by l
times than s~.
This conclusion follows from statement 2, which implies that a layer structure with a lower
period Sl proves to be more stable.
The irreducible fractions Cpst whose denominator is a period s~ form a discrete series of
values. Figure 3 shows ~b(sl, c~t) calculated from eq. (2.5.20) for such a series of irreducible
st within the range
fractions, cp,
0.5 < cpSt < 1
for s~ varying from 2 to 19. The other part of the plot corresponding to the cpst range from
0 to 0.5 should, according to (2.5.20), be symmetrical to one diagrammed in Fig. 3. To obtain
that part we should substitute 1 - cpst for %.st The horizontal coordinates of the ~b(s~, c~t)
maxima indicate the specific cpst values which provide the maxima of the dominant wave
amplitudes, and, consequently, the stoichiometric compositions of the most stable layer
superstructures. It follows from Fig. 3 that the stoichiometric compositions of such
superstructures form a homologous series
st m0.2 3 4 n (2.5.21)
c p = s~ ' 3 ' 5 ' 7 ' " " 2 n + 1 ....
where n = 2, 3, 4, 5 . . . . . The periods of the corresponding layer superstructures, st, as was
noted above, are denominators of the fractions (2.5.21), i.e.
s~ = 3, 5, 7, . . . , 2n - 1. . . . (2.5.22)
~{~, e:% zlo,(~.))'
qz,,
o° o %
oo •
• o \ \
• o %,
\
\
\
°oe °
\
\
\
• o
oo
FIG. 3. Dependence of the squared amplitude m o d u l u s of the dominant wave, q~ (sl, cp) on
stoichiometric composition c~ in the case o f layer superstructures. The points corresponding to
n
c~t = 2 n ~ are situated on the solid line. All other values of c~t give points located below this line.
respectively. With Cpt < 0.5 the series of the homologous compositions can be obtained from
the series (2.5.21) from the relation Cpst ~ 1 - c p .St.
123 n
cSt
P = m°
sl : 3' 5' 7' . . . . 2n -- 1' " " ' (2.5.23)
at cpSt< 0.5 where n = 1, 2, 3, . . . . The corresponding periods s~ , are the same odd numbers:
sl: 3, 5, 7 . . . . . 2n + 1. . . . (2.5.24)
Both series, (2.5.21) and (2.5.23) in fact correspond to the same but anti-isomorphic
superstructures, i.e. superstructures of one series can be obtained from those of the other by
replacing interstitial atoms with vacancies and vice versa. Another interesting fact is that, in
compliance with (2.5.22) and (2.5.24), the translational motif of homologous phases always
consists of an odd number of planes.
The above discussion suggests that the maximum magnitude of the dominant wave
amplitude is attained for a series of homologous stoichiometric compositions,
n n
st _ and st __ _ _
Cp 2n + 1 cp 2n - 1 "
The structure of the corresponding homologous series is determined by alternation of

completely occupied and completely vacant planes drawn within the interstice sublattices. The
choice of orientation of these planes is dictated by the vector k0 whereas their sequence is
determined from the clock diagram of the type such as that in Figs l(a, b).
To determine the vector k0 of the dominant wave one should know the function 2~(k)
depending on the interatomic interaction energies. As a rule these energies are unknown.
Some conclusions about the location of the function 2,(k) minima can however, be made.
Indeed, the distance between the nearest interstices proves as a rule, to be shorter than that
between the centers of touching interstitial atoms, i.e. than the interstitial atom diameter. This
means that the electron shells of the nearest possible interstitial atoms should overlap, which
should, in turn, result in strong "contact" repulsion. Bearing in mind the strong nearest-
neighbor repulsion of interstitial atoms and assuming that the remaining interactions between
interstitial atoms are much weaker, the wave vector k0 of the dominant wave which minimizes
2,(k), is expected to be located either in the point of the type of ½H0, or at a point in the
vicinity of ½H0 where H0 is the shortest reciprocal lattice vector along the direction Ho/Ho.
1
Let us find the vector k0 nearest to ~H0. As follows from eq. (2.5.6) at CpSt< 1/2,
k0 = S°Ho
s~
= So
2n + 1
H0 (2.5.25)
since, according to (2.5.24), s~ = 2n + 1. At cpSt> 1/2
k0 = SoH0 - So
sl 2n - 1 H0 (2.5.26)
because Sl = 2n - 1 [see eq. (2.5.22) where n is an integer.]

Let us determine the integer So so that the vectors
So H0 and So H0
2n + 1 2n - 1
be spaced at the shortest possible distance to ½H0 at a fixed value of n. This condition results
in the choice So = n and, thus, yields the relations
t ~ n H0 for a homologous phase with c;st = 2n n- 1 > 21

k0=
st n 1
[. 2 ~ H 0 for a homologous phase with cp 2n + 1 < 2 " (2.5.27)
The clock diagram in the cases of st = 2n + 1 with So = n and st = 2n - 1 with So = n results

in quite definite sequences of occupied and vacant planes, H0 = (hokolo), drawn in the p-th
sublattice o f interstices. The sequence is
...l[] x [ ] x [ ] . . . x i-lt [ ] x [ ] x • . . . x [ ] i-I . . . (2.5.28)
st=2n +1
for the homologous phase with
n
st _ 1 '
cp 2n +
and
tx []x []...[]x []x,x [] x []...[]x x... (2.5.29)
- - s I=2n - 1- -
for the homologous phase with
st n
cp - 2n -- 1"
The specific example of determination of the sequence of occupied and vacant planes in
the case So = n = 5 and st = 2n - 1 = 9 has been presented in Fig. l(b).
The sequences (2.5.28) and (2.5.29) show that homologous structures are characterized by
alternating occupied and vacant planes with faults falling on the boundary of each period.
A fault may be interpreted either as a plane vacancy defect when in the sequence (2.5.28) two
nearest planes prove to be vacant, or as a plane interstitial defect when in the sequence (2.5.29)
two nearest planes are occupied.
The next step of the structure determination procedure is the determination of the
generating plane, or the plane reproducing the layer phase structure. In terms of the
concentration wave formalism it is reduced to finding the wave vector k0 or, which is the same,
the reciprocal lattice H0 = (h0 kolo) denoting the generating plane. The latter, however, requires
the additional information about the interstitial atom interaction sufficient for the spectrum
2,(k) of the matrix Vpq(k) to be calculated. This enables us to find the dominant wave (a0, k0)
providing the lowest eigenvalue 2,0(k0). Once the sequence of occupied and vacant planes,
and the indices H0 = (hokolo) of this plane are known, one can find the complete structure
of the stable layer phase, to within small host atom displacements and homogeneous
distortions produced by interstitial atom ordering.
2.6. Stability of a Host Lattice with Respect to lntracrystalline Field at lts Sites
Produced by Ordered Interstitial Atoms
An ordered distribution of interstitial atoms along host lattice interstices, as a rule,
produced a heterogeneous field at host lattice sites. In this situation the chemical potentials
of host atoms may prove to be unequal to each other. Since the necessary condition of the
thermodynamical equilibrium is the equality of the chemical potential, such a system cannot
be stable. The equilibrium should be restored by equilibrating the chemical potential values
along the host lattice sites.
This equilibration may be brought about by elastic displacements of host atoms from their
ideal positions and by changes of the electron and spin states of host atoms such as electron
polarization, additional ionization, spin ordering, etc. Such a situation may be expected in
crystals with noticeable electrical conductivity, where the intracrystalline field is small since
free charge carriers provide strong screening of the potential generated by interstitial atoms.
In insulators where chemical potential variations are quite large and cannot be compen-
sated by the relaxation processes, atomic displacements and electron state changes of host
atoms, the equality of the chemical potentials of host atoms is maintained by the spontaneous
formation of structural vacancies. The most interesting cases are observed in insulating
crystals, ionic and covalent, where the typical variation of the chemical potential at host
lattice sites is usually commensurate with the sublimation energy of host atoms. In this case
the host lattice vacancies should be formed at those sites in which the intracrystalline field
generated by interstitial atoms takes on the largest values. The symmetry of the spatial
distribution of the structural vacancies should, in this case, coincide with the symmetry of
the intracrystalline field.
It is noteworthy that the production of large numbers of vacancies induced by modulation
of the intracrystalline field results in a dramatic drop in atomic density of the crystal and,
therefore, the formation of loosely packed ordered phase modification. In most cases this
modification is less stable than a closely packed one which is formed upon the host lattice
"collapse", which is neglected in the relevant model. For example, if structural vacancies
completely fill all the host lattice plane sites, this, in fact, means the removal of the host lattice
plane and, consequently, a corresponding "cut" in the host lattice. It is easy to see that a
lattice with a "cut" cannot be stable, since it restores its continuity by through a "collapse"
which results from linking of atoms situated on both sides of the "cut". Transformation of
a loosely packed modification into a closely packed one is, in particular, prescribed by the
principle of the closest packing.
Consequently, the formation of loosely packed modifications can only be expected in very
rare cases. This is especially true with ionic crystals or crystals with considerable ionic
contribution to the binding energy which always form closely packed modifications.
Covalent crystals may, however, be regarded as an exception. The directional type of the
chemical bonds in covalent crystals results in a situation when the crystal does not necessarily
form the closely packed modification and, therefore, does not satisfy the principle of the
closest packing. In such crystals, formation of a large number of structural vacancies induced
by interstitial ordering is quite possible. It is necessary, however, to emphasize that even in
this case the loosely packed phase proves to be unstable in face of high pressure. Increasing
pressure leads to the host lattice rearrangement which leads to the formation of the closely
packed polymorph. The structure of cristobalite, SiO2, may serve as illustration. The
cristobalite structure is analogous to the spinel structure which, in fact, is the fcc-based
interstitial ordered phase, MgA1204. In cristobalite, Si atoms are placed at the Mg atom
positions of the spinel whereas O atoms occupy AI atom positions of the spinel. As for the
fcc host lattice sites, they are completely occupied by O atoms in spinel, and are completely
vacant in cristobalite. Such a loosely packed structure of cristobalite proves to be possible
because of the coavlent character of the chemical binding. The cristobalite structure
completely fits the above-formulated conclusions: it is unstable in face of high pressure, and
transforms into the closely packed stishevite structure which is identical with the rutile
structure, the interstitial superstructure, TiO2, based on the bcc lattice formed by O-host
atoms.
Summing up the foregoing discussion, strong constraints for nonmetal stoichiometric
compounds can be formulated.
A chemical compound in which the intracrystalline field induced by interstitial atoms
considerably varies with host lattice sites and thus produces structural vacancies must be
rejected as unstable. However, if such a loosely packed compound is observed, its existence
may be expected only within the narrow range of the external thermodynamic parameters.
On the contrary, the necessary condition of the chemical compound stability is the
requirement for the intracrystalline field to be constant over the host lattice sites. In this case
there is no reason for the structural vacancies to be formed. The compound then has a closely
packed atomic structure and may be stable. The requirement that the intracrystalline field
is constant over the host lattice sites is a very strong constraint which radically reduces the
number of possible "candidates" for stable structures. Indeed, the homogeneous intra-
crystalline field can be only provided by exceptional conditions, a very special atomic
distribution of interstitial atoms and the special mutual location of the interstitial sublattices
and the host lattice.
The conclusion that a structure with the homogeneous intracrystalline field is the most
stable one seems to hold for real systems. This will be illustrated in detail later for oxides
based on the bcc and fcc host lattices.
As was mentioned above, the structural vacancies may not be formed in the case of small
modulation of the field along with host lattice sites. Small modulation may be expected when
the structure of the phase is nearly the structure providing a constant field along the host
lattice. In particular, structures with small modulation of the field can be produced from the
structures with a constant field by means of introducing the regularly spaced long distant
plane defects, vacancy or interstitial. In the concentration wave language, this means that
small modulation of the field along the host lattice occurs for structures whose wave vectors
of the dominant waves are nearly those of the dominant waves generating the structure with
constant intracrystalline field along the host lattice.
Let us have a closer look at the characteristics of the intracrystalline field at the host lattice
sites and its relation to the symmetry of the ordered distribution of interstitial atoms.
Let the potential generated at the host lattice site, R, by an interstitial atom occupying
the interstice (p,R'), be W p ( R - R ' ) . Then the complete potential g,(R) which is the
intracrystalline field generated by the interstitial atom distribution, n(p, R), is the sum of
potentials generated by each interstitial atom:
$(R) = ~ Wp(R - R')n(p, R'). (2.6.1)

p,R'
Making use the concentration wave representation (1.1.10) in eq. (2.6.1), we have
¢(R) = ~ Wp(R - R') ~ ?,(k)v, (p, k) exp(i27~kR')
p,R" ~,k
= ~ l,Vp(k)?~(k)v~(p, k) exp(i2~kR) (2.6.2)

a,k
or
C v
~b(R ) = v p~= Wp(O)+ ~'~,k fgp(k )?~(k )o,(p, k) exp(i2rckR ) (2.6.3)
where
I~'p(k) = ~ I4~(R) e x p ( - i2~zkR). (2.6.4)

s
The prime in the sum of eq. (2.6.3) means that the term
c
7,(O)th (p, O) = -~v v,(p, O)
which stands for the "zeroth wave",

1
v,(p,O) = ~ v v (1, 1 , . . . , 1)
is singled out.
Another equivalent representation of the field, qJ(R), may be obtained by substituting eq.
(1.1.1) into eq. (2.6.1):
qJ(R) = ~ l~p(k )a(p, k) exp(i2~kR)
p,k
= ~ IVp(O)cp + ~" IPp(k)a(p, k) exp(iZnkR). (2.6.5)

p p,k
It follows from (2.6.3) that the homogeneous intracrystalline field is not formed unless the
second term in eq. (2.6.3) vanishes. This is just the case when
c ~ I~p(0) = const
~¢(R) ~'p=l
For illustration, let us consider an interstitial phase in which interstitial atoms occupy the
octahedral sublattice in the fcc host lattice. The octahedral fcc sublattice is shifted by the
distance hoct = la 3 with respect to the fcc host lattice where a3 is a unit translation along the
[001] direction. Let interstitial atoms have a distribution described by the equation:
n(R) = ~l+ ~ (1e ,2,,*s
, + e,Z,,~s+ e,2,,;e) (2.6.6)
where a*, a~', a* are the unit reciprocal lattice translations along the [100], [010] and [001]
direction, respectively. These vectors are related to the (100), (010) and (001) points in the
reciprocal lattice of the fcc crystal forming the star, { 100}. The vector R labels the fcc lattice
sites:
R = xal + ya2 + za3 (2.6.7)
where al, a2 and a3 are unit translations in the fcc lattice along the [100], [010] and [001]
directions, respectively; (x, y, z) are coordinates of the fcc lattice sites (integers or half integers
whose sum is an integer). Substituting (2.6.7) into (2.6.6) and using the usual relation
apa* = 6pq (2.6.8)
where 6pq is equal to unity if p = q and zero otherwise, we have
n ( R ) = n ( x , y , z ) = ¼ + ~ ( e1 i2nx
+ e i2nv- + ei2m ) (2.6.9)
Equation (2.6.9) describes the interstitial superstructure: an octahedral interstice with
coordinates R +ho~t = ( x , y , z +½) is occupied by an interstitial atom if n ( x , y , z ) = 1. It is
vacant if n(x, y, z) = O.
J PM.S, 29/I-2--C
The corresponding formula is

Xl/4 [']3/4 or X [--]3
where X designates an interstitial atom and [] octahedral vacancy. If the host lattice
framework is ignored, and interstitial atoms and octahedral vacancies are considered as two
components forming a binary fcc substitutional solution, one may see that the structure X ["73
is isomorphic with the substitutional superstructure AuCu 3.
In the relevant case when interstitial atoms occupy only one sublattice (the case of v = 1),
eqs (2.6.3) and (2.6.5) are simplified. Summing over p and a as well as the "polarization
vector" o,~(p, k) can be omitted. In doing so, eq. (2.6.3) may be rewritten as
~O(R) = cl~(O) + ~' ff'(k )v(k ) exp(i2rckR) (2.6.10)
The distributions (2.6.6) and (2.6.9) are provided by

c=¼ and ~,,(a*)=~,(a*)=7(a~)=¼, (2.6.11)
the remaining amplitudes being equal to zero. Substituting (2.6.11) into eq. (2.6.10) yields
$ (R) = ¼I,V(0) + ¼I~(a * )[e '2'~'~'R+ e;2'~";R + e'~'~";R]
' I~(0) + ¼ff'(a *)[e '2~x+ e ;2"y+ e '2"~] (2.6.12)
where {x,y,z} are the coordinates of the host lattice sites. In eq. (2.6.12) the relations
W(a*) = W(a*)= W(a~)
following from the fcc lattice symmetry are used. Substituting the various permitted values
corresponding to the fcc lattice site coordinates, for example, {x, y, z } = (000), {110}, { 100},
{3 ½0}, etc, into eq. (2.6.12), we conclude that the intracrystalline field ff (R) may be either,
~, = ¼~(o)+ ¼~(a*)
or
q,2 = ¼if'(0)- ¼~(a~') (2.6.13)
The difference between them is
~,- q'2 = # ( a * )
Therefore the interstitial superstructures described by the distribution (2.6.6) certainly yields
the modulation of the potential along the fcc host lattice sites.
With metal interstitial phases where potential produced by interstitials on the host lattice
sites is strongly screened by conduction electrons, this modulation does not result in the
structural vacancy formation. The modulation is compensated by host atom displacements
and spin ordering (the latter if a host atom has a nonzero spin). The 7' phase, Fe4N ,
may serve a good illustration. (17) The V' phase has the metallic conductivity. Its structural
formula is
[N1/4 [-]3/4] Fe
and it is described by eq. (2.6.6). The modulation (2.6.12) of the potential along the fcc host
lattice sites is compensated by Fe host atom displacements.
This is not the case with covalent crystals where the modulation (2.6.12) cannot be screened
by conduction electrons and, consequently, should produce the structural vacancies in the
host lattice. The loosely packed NbO phase may serve as another example. (18)The structural
formula of this phase is
[Nb3/4 ["]1/4](O3/4 [] 1/4)
where [] designates the structural vacancy in the fcc host lattice formed by O-atoms.* In
this phase the distribution of octahedral vacancies, [] and fcc host lattice vacancies, [ ] , is
described by the same eq. (2.6.6).
Another example of a loosely packed nonmetal compound described by eq. (2.6.6) is
ReO3 .09) Its structural formula is
[Re1/4 [] 3/4](03/4 [] 1/4) = Rel/403/4 • (2.6.14)
The distribution (2.6.6) describes the positions of Re-atoms in the octahedral sublattice and
structural vacancies, [], in the fcc host lattice formed by O-atoms.
The loosely packed ReO 3 structure should be unstable in face of high pressure transforming
it into a closely packed polymorph. It can, however, be stabilized by removal of the structural
vacancies which can be accomplished by introducing atoms of the third kind into the oxygen
vacancies. Substituting in (2.6.14) the metal atoms M ~1)for the oxygen vacancies, [], and the
metal atoms M <2) for Re, we have
[Mt~)4[] 3/4](03/4 M~)4) = Mt~)4Mt~)403/4 (2.6. t 5)
i.e. the formula M(1)M(2)O3. Formula (2.6.15) and the associated structure gives the
wide-spread perovskite structure. The perovskite structure is, in particular, realized with the
classic ferroelectric, barium titanate, BaTiO3 .(:°-:4)
2.7. Host Atom Displacements Induced by Interstitial Ordering

All the calculations in the previous sections were carried out within the framework of the
rigid lattice model. The rigid lattice model completely neglects the elastic displacement
relaxation of the host lattice caused by interstitial atoms. In reality, each interstitial atom is
a source of the displacement field, and the resulting field is the sum of the displacement fields
generated by all interstitial atoms. This is the reason why the host atom displacements depend
on the interstitial atom configuration and, therefore, on the type of the ordered distribution
of interstitial atoms.
To refine the chemical compound structure, one must know all atomic coordinates, i.e. all
the host atom displacements generated by interstitial atoms. Since we want to have an insight
into the elastic displacements caused only by ordering, it is convenient to choose the state
of the so-called "average crystal" as the reference state of the host lattice. The "average
crystal" is a hypothetical perfect high symmetry crystal whose host lattice sites form an ideal
homogeneous lattice associated with the completely disordered state (the lattice in which all
host atom displacements generated by concentration fluctuations are assumed to be zero).
According to this definition of the reference state, all host atom displacements caused by
ordering are counted off from the crystal lattice sites of the "average crystal".
It is clear that each concentration wave generating the ordered state should, in a general
case, induce a static displacement wave in the host lattice. Since the translational symmetry
*The symbolsin the brackets describethe relation betweeninterstitial atoms and their vacancies,the symbolsin
the parenthesis describe the relations between host atoms and structural vacancies in the host lattice.
of both waves coincides, the displacement wave and concentration wave are characterized by
the same wave vector. Therefore, the purpose of any theory of atomic displacements in a
superstructure is the finding of the functional relation between the amplitudes of static
displacement waves and concentration waves.
It follows from the above discussion that the arising of a concentration wave
7~(k) v~(p, k ) exp (i2ztkR) (2.7.1)
with the wave vector, k, induces the displacement wave
w~(k ) exp(i2hkR ) (2.7.2)
in the host lattice with the same vector k. The amplitude of the displacement wave, w~(k)
is a function of the amplitude of the concentration wave, y~(k) inducing it, i.e.
w,(k) = w, (k, v~(k )). (2.7.3)
In weak interaction of concentration waves and displacement waves, the function w,(k, v~(k))
may be represented by the first nonvanishing term in the Taylor expansion into the power
series of 7,(k). With all other terms neglected, eq. (2.7.3) becomes
w,,(k ) _~ w°(k )7~(k ) (2.7.4)
where w°(k ) is the first-order expansion coefficient. The expansion (2.7.4) represents the linear
response approximation. It will be shown in this section that the linear response approxi-
mation (it is also referred to as the superposition approximation) holds in the framework of
the linear microscopic theory of elasticity. (8'6) The linear theory of microscopic elasticity may
be used only to estimate the displacement field because it may provide just the first
approximation of the theory. We have to employ this approximation because the accurate
calculation is an extremely complex problem, requiring detailed information about the
interatomic interactions.
In spite of its approximate character, the linear elasticity approach may be useful in many
cases. For example, if an amplitude of the displacement wave, w,(k), calculated in the linear
approximation is directed along one of the symmetry direction of the crystal, it is a result
of the symmetry of the reciprocal lattice point corresponding to the wave vector, k, rather
than the concrete form of the interatomic interaction potentials.* This is precisely the reason
why in this case the direction of w~(k) is always correctly determined whatever the accuracy
of the approximation employed. In other words, the approximate nature of the linear
elasticity model may manifest itself only in the accuracy of the value of the calculated
magnitude of the displacement wave amplitude rather than in the accuracy of its direction
determination.
To calculate the coefficient w°(k) which is the coupling constant between host lattice
displacements and concentration fluctuations, we employ the expansion of the elastic strain
energy A~b of an interstitial superstructure into the power series of host atom displacements,
u (R), and of interstitial atom density fluctuations, An (p, R) = n (p, R) - n, where n = c/v ~6)
1
A~ = - ~" f ( p , R - R ' ) u ( R ) A n ( p , R ' ) + - ~ R ~ Aij(R-R')ui(R)uj(R'). (2.7.5)
p,R,R' , '
The subscripts i, j = 1, 2, 3 are the Cartesian coordinate indices and Aij(R - R') is the
Born-yon Karman tensor of the host lattice (25) which characterizes the rigidity of the host
*In a general case, one may neglect the highly unrealistic assumption that the high symmetrydirection of the
amplitude, w,(k), proves to be a result of favorable specificchoice of the relation between interatomic interaction
potentials.
lattice against displacements. The set of Born-von Karman constant A i j ( R - R'), is the
fundamental characteristic of the dynamic properties of a crystal because it determines the
vibration frequency spectrum. The coupling parameters, f(p, R - R') are the so-called
Kanzaki forces with which the interstitial atom at the (p, R') interstice acts on a host atom
at the site R of the undisturbed host lattice. The forces f(p, R - R') are material constants
that describe the ability of interstitial atoms to distort the environmental host lattice. It is
easy to see that eq. (2.7.5) is but a second-order Taylor expansion of the elastic energy into
the power series of the displacements u(R) and concentration heterogeneities An(p, R "). This
"harmonic" approximation corresponds to linear microscopic elasticity. Equation (2.7.5)
holds in the case of Bravais host lattices.
Minimizing the elastic energy (2.7.5) with respect to displacements u(R) yields the
equilibrium equation
~, A~j(R - R')uj(R') = ~ f~(p, R - R')An(p, R') (2.7.6)

R' p,R'
Multiplying eq. (2.7.6) by e x p ( - i 2 n ( k R ) ) and summing over R, we obtain the equation for
Fourier transforms:
~,j(k) wj(k) = F,(p, k)a(p, k) (2.7.7)

where
Aij(k ) = ~., A~j(R ) e x p ( - i2nkR ) (2.7.8)

R
is the dynamic matrix,
F(p, k) = ~ f ( p , R) e x p ( - i 2 n k R ) (2.7.9a)
R
a(p,k)= 1 ~ An(p,R)exp(-iZ~kR) (2.7.9b)
w(k ) = 1 ~ u(R)exp(-iZ~kR), (2.7.9c)
N is the total number of the host lattice sites. The solution to eq. (2.7.7) for the Fourier
transform w(k) is
w,(k) = Go(k ) ~ Fj(p, k)a(p, k) (2.7.10)

P
where Gij(k) is Green's tensor which is the inverse of the dynamic matrix .4u(k)
Gij(k )Ajk(k ) = 6o (2.7.11)
where 6ij is the Kronecker symbol (6~j= 1 if i = j and zero if i :~j). The Hermitian tensor
Gij(k) can be written in terms of eigenvectors, e~(k), and eigenvalues, mto2(k), of the dynamic
matrix, Aij(k):
=3 e~(k)e*J(k)
oij(k) = ,=,Z m~o~(k) (2.7.12)
where e~(k)= (e~,e2, e 3) is a unit polarization vector of the vibration acoustic mode
characterized by the polarization, u, wave vector, k, and frequency ~o~(k). The constant m
is the mass of the "average crystal" per Bravais lattice site.
It should be emphasized that in the linear microscopic elasticity theory, the interstitial atom
displacements are assumed to be equal to zero.
Assuming Go(k) to be a matrix element of the operator 6~(k), we may rewrite eq. (2.7.10)
in the symbolic form:
p=v
w(k) = d(k) ~ F(p, k)a(p, k). (2.7.13)
p=l
Equation (2.7.13) completely determines the host atom displacement field induced by
interstitial atom heterogeneities.
Let us consider a particular case when the concentration heterogeneity is provided by the
concentration wave (2.7.1). One may readily see that for this wave
a(p, k) = ~ ( k )o~(p, k ). (2.7.14)
w~(k)=[~(k)~F(p,k)~(p,k)]?~(k). (2.7.15)
Comparing eqs (2.7.15) and (2.7.4) yields
w°~(k ) = G~j(k ) ~.. F:(p, k )v.(p, k ) (2.7.16)

P
or
w°(k) = ~,(k ) ~ F(p, k )o~(p, k) (2.7.17)
p
Equations (2.7.16) and (2.7.17) determine the coupling parameter, w°(k), between the
amplitudes of the displacement wave and concentration wave. In the linear elasticity
approximation the displacement field of host atoms is described by the inverse Fourier
transform
u (R) = ~ w 0(k) ?, (k) exp (i2r~kR) (2.7.18)
tr,k
The direct calculation of host atom displacements by eq. (2.7.18) is possible if the coupling
parameters, F(p, k), characterizing the interaction between displacement waves and concen-
tration waves, are known. These coupling parameters were calculated through the concen-
tration crystal lattice expansion coefficients in the cases of octahedral and tetrahedral
interstices in the bcc and fcc host lattices. (26'6) When interstitial atoms occupy octahedral
interstices of the fcc lattice, we have
Fo~f~t(k) = - t -. ~a~cc (cH + 2c12) ~daf~ (sin nkx, sin rcky, sin 7rkz) (2.7.19)
where ar~ is the fcc lattice parameter, Cl~ and c~2 are elastic constants, (kx,ky,k~) are
dimensionless components of the wave vector
k = kxa* + kya* + k~a*, (2.7.20)
1 daf~ is the host lattice expansion coefficient.

af~ dn
If interstitial atoms occupy tetrahedral interstices in the fcc lattice,
/~t~toer(l, ~)x ~- -- ia~ce(Cll 't- 2C12) ~ exp i ~ (k~ + ky + kz)

l
x ( sin-~kxCOS-}kycos-~kz+icos-~kxsm
n n rc n " -2n kys i n 2n kz )
F~t~(1, k )>,= - ia ~ (c~, + 2q2) ~ exp + i ~ (k~ + ky + k~)
x sin ~ ky cos ~ k z c o s ~ k x + i cos~ ky sin ~kz sin ~ kx
fo: k)~ = - ia~(Cll + 2c12) dafoe exp [ i ~rt (kx+ky+kz) 1

Ftetr(1,
aloe dn
( 7¢ 7~ 7Z 7Z. 7Z 7~ )
x sin-~k~cos~kxcos-~k,+ icos~kzsm-~k, sin-~ky (2.7.21)
foe k) is related to the first sublattice of tetrahedral interstices displaced by
The vector Ft,tr(1,
the vector
hi = ~(al
1 + a2 + a3)
with respect to the host lattice.
The vector Ft~tr
f~ (2, k ) related to the second sublattice of tetrahedral interstices displaced by
the vector
/I2 = _ ¼(al -+- a 2 q- a 3)
with respect to the host lattice. It can be obtained from Ftetr(1
f~ , k ) by using the relation
fcc fec
Freer(2, k) = -Ftetr(1 , - k )
Equations (2.7.19) and (2.7.21) hold in the nearest-neighbor interaction approximation. In
the case, when interstitial atoms occupy octahedral interstices of the bcc host lattice
boe(3, k) = - ia2cce -i"k~ (all sin nk~ cos ~zky, all sin nky cos nkx, tr33sin rck~) (2.7.23)
Fo~t
where
da~ dc
al, = (c, + c 1 2 ) ~ + c l 2 - -dn
c
dc dab~
0"33 = CII ~ "]- 2C12 ab~ dn
dat,¢/a~c dn and dc/c dn are the host lattice expansion coefficients along the [100] and [001]
directions, respectively, if interstitial atoms occupy the p = 3 sublattice of octahedral
interstices whose sites are located between the nearest host atoms in the [001] direction. The
vectors, Fo~t(1,
b~o k) and F ~ ( 2 , k) may be obtained from (2.7.23) as a result of cyclic
simultaneous permutation of all components of the Fo~(3, b~ k ) and k vectors:
bcc
Foct (1, k) = - i a ~ e -i~kx (0"33 sin nkx, O'll sin 7zky cos nkz, trlt sin nk~ cos rckr)
bcc(2, k) = - ia~c~e-~k~ (a. sin nk, cos nkz, a33 sin 7zky, o"n sin nkz cos nk,).
Fo~t (2.7.24)
Equations (2.7.23) and (2.7.24) are derived in the nearest and next-nearest-neighbor
interaction model.
2.8. Secondary Ordering in Nonstoichiometric Compounds

If the composition of a chemical compound differs from the stoichiometric composition
of the stable superstructure which will, for brevity, be called the primary superstructure,
partial disordering arises. Excess of interstitial atoms results in the random occupation of the
"forbidden" interstices of the primary superstructure, whereas the deficiency of interstitial
atoms results in a situation when the "permitted" interstices occupied by interstitial atoms
in the primary superstructure are partially filled with vacancies. Such nonstoichiometric
disordered solid solutions based on the primary superstructure cannot be stable at low
temperatures and undergo either secondary ordering or secondary decomposition. Both
processes lead to the formation of completely ordered stoichiometric phases. If, however,
these processes do not occur, the Nernst principle would be violated: according to the Nernst
principle, a nonstoichiometric and, therefore, partially disordered superstructure cannot be
stable at 0°K.
To find the structure of a secondary phase which should arise as a result of secondary
ordering or decomposition, one must consider either ordering of nonstoichiometric vacancies
in the "permitted" sublattice (assuming deficiency of interstitial atoms), or the secondary
ordering of excess interstitial atoms within the "forbidden" sublattice of the primary
superstructure (under the conditions of excess of interstitial atoms) and determine the most
stable secondary superstructure.
The analysis of the secondary superstructure is carried out by the same method as the
analysis performed in Sections 2.2 to 2.5 for a primary superstructure. The only difference
is that the number of interstices in the cases where secondary ordering occurs proves to be
reduced due to the ordering leading to the primary superstructure.
The locus of the "permitted" interstices in a primary superstructure is defined by the
equation
no(p, R) = 1 (2.8.1)
where no(p, R) are occupation probabilities to find interstitial atom at the (p, R) interstice
in the case of the primary superstructure. Let us label the positions of interstices meeting eq.
(2.8.1) by indices {p, r}. The remaining interstices where no(p, R ) = 0, are "forbidden" for
the primary superstructure. Therefore, all the equations derived in Sections 2.1 and 2.5 prove
to be valid if coordinates of interstices {p, r } are substituted for {p, R } and if the fact that
the secondary ordering of vacancies occur only in the "permitted" interstices {p, r} (in the
case of interstitial atom deficiency) is taken into account.
As with the theory of secondary ordering in substitutional solutions, (~ one may demon-
strate that the Fourier transform of the interatomic interaction matrix, Vpq(k), should be
transformed when the transition from the set of sites {p, R } to the set {p, r} is made. The
new matrix ~'pq(k) is
Vpq(k ) = ~. Vpq(k - ks)y°(k,)o°(p, ks) (2.8.2)
a,k s
where the coefficients y°(k,) and v°(p, ks) enter the distribution function no(p, R), describing
the primary superstructure by the equation
no(p, R) = ~ y° (ks)O° (p, k,) exp(i2rcksR ). (2.8.3)

o,s
The matrix, Vpq(k) and its eigenvalues, ~[,(k), must be substituted for the matrix Vpq(k) and
the eigenvalues 2,(k) in all the equations in Sections 2.1 to 2.5. This approach will be
employed below in the analysis of the structures of transitional metal oxides.
3. STABLE STRUCTURES OF TRANSITIONAL METAL OXIDES BASED ON THE BCC HOST

LATTICE FORMED BY OXYGEN ATOMS
The energy and structural concepts proposed in Section 2 enable us to reduce the structure
determination procedure to the following steps:
(1) Determining the dominant concentration waves {a0, k0} generating according to eqs
(2.3.1) and (2.4.1) the stable primary superstructure.
(2) If the stoichiometric composition of the derived primary superstructure does not fit the
valencies of the constituents, a certain number of interstitial metal atoms must be removed
to restore the interstitial-to-host atom ratio required by valencies. The resulting interstitial
atom vacancies are situated in the "permitted" interstices of the primary superstructure. They
may undergo secondary ordering decreasing further the configurational energy of the system.
The superstructure formed in such a secondary ordering can be determined in the same way
as the primary superstructure was. The only difference is that the new interaction matrix
Wpq(r - r ' ) , its eigenvalues, £,(k) and the densities, n(p, r), should not now be determined
over all initial bcc host lattice interstices, {p, R }, but only at the set of "permitted" interstices,
{p, r }, of the primary superstructure.
(3) If the stoichiometric composition nevertheless does not fit the valency rule, operation
2 should be repeated, i.e. the tertiary, quaternary and so on ordering should be carried out
until the stoichiometric composition eventually fits the valency rule. Such a final super-
structure describes the atomic structure of the stable oxide. This procedure will be described
in detail below in the analysis of oxide structure formed as the result of an ordered
distribution of metal atoms over interstices of the bcc host lattice composed of oxygen atoms.
3.1. Interaction of Interstitial Atoms in the bcc Lattice

Let interstitial atoms occupy octahedral interstices of the bcc host lattice. There are three
octahedral interstices, Ox, Oy and O~, per host atom. These interstices are displaced by
[a/2, O, 0], [0, a/2, 0] and [0, 0, a/2] from the host atom, respectively (Fig. 4) where a is the
bcc lattice parameter. Translation of each of these three interstices generates its own bcc
sublattice of octahedral interstices. These sublattices Ox, Oy and Oz will be enumerated by the
indices p = 1, 2, 3. Any octahedral interstice that can be occupied by an interstitial atom has
four nearest octahedral interstices removed from it by rl = a/2, eight interstices in the second
coordination shell at a distance of r2 = a/x/~, eight interstices in the third coordination shell
removed by r3 = a x//3/2 and six interstices in the fourth coordination shell removed by r 4 a. =
FIG. 4. Octahedral sites in the bcc lattice. • , O x interstices. The tetragonal axis is along the [100]
direction. Q, Oy interstices. The tetragonal axis is along the [010] direction. (]), Oz interstices. The
tetragonal axis is along the [001] direction.
Following the mechanism formulated in Section 2, stable ordered distribution of interstitial

atoms is determined by the dominant waves {a0, k0 } associated with the minimum eigenvalue
of the matrix Vpq(k) which may generate a superstructure without complementary non-
d o m i n a n t waves. The elements of such a matrix depend on interaction energies of interstitial
atom pairs. Therefore to analyse the atomic structure of a specific system, some model of
interstitial atom interaction should be assumed. The data on interatomic interactions in
oxides are rather scarce but some plausible assumptions may, however, be made.
X-ray studies reveal that the typical distance between oxygen atoms in nonmetal oxides
is of the order of 2.7 to 3.2 ,~. In the case when the bcc host lattice is composed of oxygen
atoms the shortest distance between them is a ,/~/2. The latter enables us to estimate the
parameter a. It is within the range of 3.1 to 3.7 A.'The separation distance between the nearest
octahedral sites, r~ = a/2, is thus within the range of 1.55 to 1.85 A, which is less than the
atomic diameter of most metals. Consequently, electron shells of two metal atoms introduced
into the nearest octahedral interstices of the bcc host lattice overlap. In this situation the
"contact" repulsion should far exceed all other interaction energies.
Interaction of more distant neighboring metal ions which are not separated by oxygen
atoms seems to be close to the Coulomb interaction in most ceramic oxides. Interactions of
metal ions at large distances are much weaker since electrostatic interactions between them
are screened due to atomic displacements and polarization of oxygen atom electron shells.
The screening effect therefore, if it occurs, enables us to utilize the short-range interaction
model neglecting the interaction of long-distant metal ions.
Summing up the foregoing, let the repulsion energies of metal atom interaction at the
distances r~, r2, r3 and ra be denoted as WI, W2, W 3 and W4, respectively. The following
relations between the interaction energies may be assumed
W 1> W2> W3> W4>0 (3.1.1)
The interaction energies of metal atom pairs separated by larger distances will be assumed
to be equal to zero. We shall thus proceed from the assumption the relations (3.1.1) between
interaction potentials of interstitial atoms determine the basic structural characteristics of
oxides built as the bcc-based interstitial superstructures.
The Vpq(k) matrix (2.1.5) in the case of three octahedral sublattices of the bcc host lattice
has the form
/Vll,(k) gi2( k ) g13 ( k ) \
Vpq(k)=lV~2(k ) V22(k) V23(k)~ (3.1.2)
\V*(k) V*(k) V.(k)/
since, according to (2.1.6), V21(k) = V*(k) and V32(k) = V~3(k). The elements of the V,q(k)
matrix may easily be calculated within the framework of the short-range interaction model
(3.1.1). Substituting the interaction energies 1411, W2, W3 and W4 and the corresponding
octahedral interstice coordinates into eq. (2.1.5), we obtain
VII (k) ~- V22 ( k ) ~- V33( k ) = 8 W 3 cos 7~kx cos 7"~kycos 7~kz
+ 2 W4(cos 2rckx + cos 27~ky+ cos 27~kz) (3.1.3a)
Vl2(k ) = [2W1 cos 7rkz+ 4W2 cos nkx cos 7~ky]exp(iT~(kx - ky)) (3.1.3b)
V13(k) = [214/"1cos nky + 41412cos nkx cos nkz] exp(iTr(kx - kz) ) (3.1.3.c)
Ve3(k ) = [2Wl cos 7rkx + 4W2 cos 7ckycos 7rk~] exp(irc (ky - k~) ) (3.1.3d)
where
k = kxa* + kya* + kza* (3.1.4)
and a*, a*, a~' are unit reciprocal lattice vectors corresponding to the (100), (010) and (001)
points of the reciprocal lattice of the bcc host crystal.
3.2. Interstitial Superstructures in the bcc Host Lattice. Titanium Oxides

Let us consider the examples of titanium oxides which may be treated as interstitial
superstructures based on the bcc host lattice composed of oxygen atoms. As is known,
titanium valency is within the range + 3 to + 4. The stoichiometric formulae of oxides with
valencies of + 3 and + 4 are Ti203 and TiO2, respectively, and oxides formed by Ti atoms
in other valent states have intermediate stoichiometric compositions. The Ti/O ratio in the
phases under consideration thus varies in the range
1/2 ~< Ti/O ~< 2/3. (3.2.1)
There are four types of dominant waves which can be used in eq. (2.3.1) to generate stable
primary superstructures meeting the maximal amplitude principle. The first dominant wave
which may generate the superstructure without nondominant waves is
1
o2(p, 0) = (02(1,0) 02(2, 0), 02(3,0)) = ~ (I, I, 2) (3.2.2)
The dominant wave (3.2.2) has a wave vector k0 = 0 and an eigenvalue

22(0) = Vu(0) - V~2(0) = - 2 W 1 - 414,'2+ 8W3 (3.2.3)
of the matrix (3.1.2) if interaction in three coordination shells is taken into account.
The remaining possible dominant waves have wave vectors along the [111] directions in the
reciprocal lattice. As was shown in Section 2.4, the wave vectors meeting the maximal
amplitude principle are
ko = H/sl where sl = 2, 3,4 (3.2.4)
H is a reciprocal lattice vector of the bcc host lattice. Bearing in mind (3.2.4) and the fact
that the vector H in eq. (3.2.4) lies along one of the [111] direction, one may see that the vector
k0 may assume the following values*
k 0 = ( l l l ) , (2/3, 2/3, 2/3), (1/2, 1/2, 1/2) (3.2.5)
The corresponding dominant waves which may generate the superstructures without com-
plementary nondominant waves are
01(p, ko) exp(i2zckoR )
= (ol (1, ko), Ol (2, ko), ol (3, k o)) exp (i2nk oR )
1
=~-~(1,1,1)exp(i21t(x +y +z)) at ko=(lll ) (3.2.6a)
ol(p, ko) exp(i27rko R)
= (1, 1, 1) exp t ~ - (x + y + z) at k0 = (2_3i32

z) (3.2.6b)
*For brevity, the designations k = (kxkykz) and H = (IIxHyHz) instead of the correct one k =-1 (kxkykz) and
1 a
H = - ( H x H y H z ) will be used.
a
vl (p, ko) exp(i2rckoR )

1
- /--(1, 1, 1 ) e x p ( i n ( x +y +z)) at k0=(½~½) (3.2.6c)
where
R = xal + ya2 + za3. (3.2.7)
al, az, a3 are the unit bcc host lattice translations along the [100], [010], [001] directions,
respectively. The concentration waves (3.2.6) are characterized by the eigenvalues
21 (k0) = Vll(ko) + 2V12(ko). (3.2.8)
Making use of the matrix elements (3.1.3) in (3.2.8), we have
4 W 1 + 8 W 2 - 8 W 3 at k 0 = ( l l l )
21(k0)=
{0 W I + W 2 - W 3 at k0 ~"k3
at k0 = ½).
t~-2z)
33
Since W~ far exceeds the remaining interaction energies, it follows from (3.1.3) and (3.2.3)
(3.2.9)
that
,~l(k~)111)) < ,~2(0) < ,~l(kg ~232)) < ,~l(k (½½½)) (3.2.10)
In compliance with (3.2.9) the lowest energy superstructure should be generated by the
concentration wave (3.2.6a) with a wave vector k(0'm = (111). Substituting eq. (3.2.6a) into
eq. (2.3.1), we have
no(p, R ) = 3 + 71 (k (111))°1 (P, k(0111))eiZ~k(°l")R

c
= ~ + 71(k(0m))
5 (1, 1, 1) exp(i2rc(x + y + z ) )
c
no(1, R ) = 5 + 71(k(ol'l)) exp(i2r~(x + y + z ) )
= n0(2, R) = -t-71(k(olll))-5--/~exp(i2g(x + y +z)) (3.2.11)
C 1
B0(3, R ) = ~ + 71 ( / ( 1 1 1 ) ) ~ exp(i2~ (x + y + z)).
The function no(p, R) is either 0 or 1, only in the case of c = Cst = 3/2 and 71 (k~1H)) = x/~/2.
Then
n0(1, R) = no(2, R) = n0(3, R) = ½+ ½exp(i2rc(x + y + z)). (3.2.12)
Substituting the coordinates {x,y,z} of the bcc host lattice sites R (for instance,
{x,y,z} = (0,0,0), (1/2, 1/2, 1/2), (100), (3/2, 1/2, 1/2) etc.) one may readily see that the
function (3.2.12) assumes only two values, 0 and 1. Placing Ti atoms in octahedral interstices
{p, R} where no(p, R ) = 1, we obtain the Ti302 superstructure. The stoichiometric primary
superstructure Ti302 in fact cannot exist since its composition does not fit the valencies of
constituents, and its cst = Ti/O ratio being equal to 3/2 is beyond the range (3.2.1). To shift
the Ti/O ratio into the acceptable range (3.2.1), some of the Ti atoms of the primary
superstructure Ti302 should be removed. An additional reduction in the configurational
energy can be achieved by secondary ordering of the resultant titanium vacancies over the
"permitted" interstices of the primary superstructure. The maximal amplitude principle for
a secondary superstructure is provided when secondary ordering of vacancies is generated by
only a sole dominant wave. The latter may, however, occur under very specific conditions:
it is necessary for the eigenvector of a secondary ordering dominant wave to be
1
o~0(p, kl)=~--~ (1, 1, 1) (3.2.13)
where k~ is the wave vector of the secondary dominant wave. Otherwise the atomic
distributions in the Ox, Oy and Oz interstices would, unlike the case of primary superstructure
Ti302, be different, and the nondominant wave with kl = 0 describing the interstitial atom
redistribution between the Ox, Oy and Oz sublattices must be introduced in the distribution
of the kind of (2.3.1). The eigenvector (3.2.13) is realized only at
k = k~ = (k~k~kx). (3.2.14)
Indeed, according to eq. (2.8.2), the matrix Vpq(k) for the secondary ordering is
/p.(k)
epq(k):l~2(k ) ~,~22(k)1"~23 (k) J (3.2.15)
\v*3(k) v*3(k) Y.(k)/
where
¢'.q(k ) = ½[Vpq(k ) + Vpq(k - ko)] (3.2.16)
and ko = (111).
At k = k i = (kxkxkx) the matrix (3.2.15) is simplified:
. / 1"~il(kl) ~'~12(/1) ~'~12(kl)~
Vpq(kl) = [ ffl2(kl)* Pll(kl) (12(kl)l (3.2.17)
\ ~,~12(kl)* ~'~12(/1)* Vll(/l) /
Its eigenvalue
~[,(k,) = 171,(k,) + 2171z(k,) (3.2.18)
is really associated with the eigenvector (3.2.13). Making use of (3.1.4), (3.2.14) and k o = (111)
in (3.2.16), we have
lTll(kl) = 0 1712(/1) = 4W 2 cos nklx cos nkly = 4W 2 cos2/zkx . (3.2.19)
~[t(kt) = 4W2 cos27zkx> 0. (3.2.20)
Equation (3.2.20) shows that ~[1(kl) ~>0 i.e. secondary superstructure meeting the maximal
amplitude principle would result in an increase in the configurational energy of the system.
In other words, secondary superstructures based on the hypothetical primary superstructure
Ti302 and fitting the inequalities (3.2.1) for Ti atom content cannot be formed. This is the
reason why we have to consider an alternative dominant wave (3.2.2) generating another
primary superstructure without complementary nondominant waves.
Using eq. (2.3.1), we may write

c c 1
n0(p, R) = -~ + Y2(0)u2(p, 0) = ~ + ),2(0) ~-~ (L T, 2)
c 1
n0(1, R) -- ~ - y2(0) V/~ (3.2.21)
c 1
= no (2, R ) = -~ - Y2 (0)
c 1
no(3, R) = 3 + 2)'2(0) ~ .
The function no(p, R) in (3.2.21) assumes only two values, 0 and 1, in two cases:
(i) when c = c s t = 1 and )'2(0)=--~-- and
(ii) when c =cst=2 and )'2(0)- x/~

3
In the case (i) we have
no(p, R) = -~ + --~ o2(p, 0) = (no(I, R), no(2, R), no(3, R)) = (0, 0, 1)
i.e.
no(I, R) = 0, no(2, R ) = 0, no(3, R) = 1 (3.2.22)
In case (ii) eq. (3.2.21) yields
no(p,R) =-2 _ ~/6 o2(p, 0 ) = (no(1,R),no(2, R),no(3, R))=(1,1, O)

3 3
i.e.
n0(1, R) = 1, n0(2, R) = l, n0(3, R ) = 0 (3.2.23)
The function (3.2.22) describes the superstructure TiO where interstitial Ti atoms completely
fill the Oz sublattice (p = 3) whereas the Ox and Oy sublattices of octahedral interstices
(p = 1, 2) are vacant [Fig. 5(a)]. The function (3.2.23) describes the primary superstructure
in which Ox and Oy interstices are completely filled, and O. interstices are vacant. Note that
Ox and Oy interstices filled with interstitial atoms together make up the primitive tetragonal
lattice whose parameters, a, b and c, are equal to a/x/~, ½a and a/w~2, respectively and are
directed along the [110Ibm, [001]b~ and [li0]b~c axes, respectively [see Fig. 5(b)].
The cst -- Ti/O ratio corresponding to the distribution (3.2.22) is equal to l, and the Ti/O
ratio corresponding to the distribution (3.2.23) is equal to 2. Both Ti/O ratios are out of the
range (3.2.1).
To shift the Ti/O ratio into the range (3.2.1) allowed by the valencies of the constituents,
a certain part of Ti atoms should be removed from the primary stoichiometric superstructures
depicted in Figs 5(a, b). An additional energy decrease may be attained by secondary ordering
of vacancies formed in "permitted" interstices of the primary superstructure following the
removal of excessive Ti atoms.
Therefore, secondary ordering should occur over Oz interstices in the superstructure
depicted in Fig. 5(a), and over Ox and Oy interstices in the primary superstructure depicted
on Fig. 5(b). These two superstructures are thus "predecessors" of two families of secondary
{b}
T 1
FIG. 5. (a) The MO superstructure generated by the vector k 0 = 0 in accordance with the distribution
function (3.2.22). O, Oxygen atoms; O, metal atoms. (b) The primary superstructure M20 generated
by the vector k0 = O in accordance with the distribution function (3.2.23). O, Oxygen atoms; O,
metal atoms.
superstructures formed by ordering nonstoichiometric vacancies over the "permitted"

interstices of the primary structures.
A certain clarification should be made concerning the secondary superstructures derived
from the primary superstructure displayed in Fig. 5(a). In all of them, interstitial Ti atoms
occupy only the octahedral sublattice, Oz. Because of the large radius and high content of
interstitial Ti atoms, the considerable tetragonal extension of the bee host lattice along the
[001]b¢¢ axis should be produced.* It should, however, be remembered that the bee host lattice
becomes unstable if the tetragonal extension proves to be too high. A tetragonally distorted
bee lattice having an axial ratio c/a = x/~ ~ 1.41 is known to be in fact merely the fee lattice.
Therefore, the strong tetragonal distortion generated by Ti atoms in a secondary super-
structure derived from the primary superstructure shown in Fig. 5(a) results in the bee --* fee
host lattice rearrangement.
The estimation carried out within the hard sphere model at rTi = 1.44 and ro = 1.40 .~ for
Ti and O atoms, respectively, gives the upper concentration limit for the bee host lattice
stability. It is equal to Co = Ti/O = 0.29. The Ti atom content at Ti/O < 0.29 is, however,
outside the range (3.2.1) and therefore does not fit the valencies of its constituents. This means
that structures based on ordered distributions of Ti atoms over Oz interstices of the bee host
lattice cannot exist. They undergo the bee~fee host lattice rearrangement to produce
superstructures based on the fee host lattice.
The diffusionless bee--* fee host lattice rearrangement of the structure shown in Fig. 5(a)
results in the classical NaCl-structure (see Fig. 6). In principle, the stable bee-based
stoichiometric primary supersturcture MO presented in Fig. 5(a) could be expected for
divalent metals. But this primary superstructure would immediately transform into the
NaCl-structure. In complete agreement with this conclusion the NaC1 structure is one of the
most frequently occurring structures for most divalent oxides (MgO, CaO, BaO, ScO etc.
[27]). The b e c k fee instability of the host lattice is also the reason for all secondary
superstructures arising in the nonstoichiometric primary superstructure described by eq.
(3.2.22) to be derived as secondary superstructures in the fee-based NaC1 structure rather than
in the primary bee-based superstructure (3.2.22). This is why all these secondary structures
*The insertion of interstitial atoms into Ox, Oy and 0 z interstices having the D4h point symmetry is known to
produce tetragonal extension of the bee host lattice along the [100]~, [OlO]b~ and [001]~ directions, respectively.
FIG. 6. Formation of the NaCl-type structure from the MO bcc-based superstructure of Fig. 5a due
to the tetragonal distortion. O, Oxygen atoms; 0 , metal atoms.
will not be considered here since we discuss in this section superstructures based on the bcc
host lattice only. The "predecessor" of the bcc-based superstructures is the primary
superstructure described by eq. (3.2.23). This primary superstructure cannot be observed at
the stoichiometric state since its cst = Ti/O = 2 ratio is outside of the permitted range (3.2.1).
Non-stoichiometry arises due to removal of part of Ti atoms to shift the Ti/O ratio into the
range (3.2.1) and to form corresponding structural vacancies. Structural vacancies of Ti
atoms, in turn, undergo secondary ordering over "permitted" Ox and Oy interstices of the
primary superstructure.
Since in the primary structure (3.2.23) the Ox and Oy sublattices are only permitted to be
filled by interstitial atoms (p = 1 and p = 2), the Vpq (k) matrix has the simplified form
Vpq(k) = ( V i i ( k ) Vl2(k)'~ (3.2.24)

V,2(k)* v22(k)J
where the matrix elements are given by eq. (3.1.3).
The matrix (3.2.24) has two branches of eigenvalues:
2t+)(k)=l[v,,(k)+ V22(k)] -+ _~/IV"(k)-~- V22(k)12+ I V,2(k)[ 2" (3.2.25)
Since we are interested in minimum eigenvalue, the lower branch will be considered. It is
2(_)(k ) = ½[Vll(k ) + V22(k)] - ___~/[VH(k) -- V22(k)12]+ I V12(k) 12. (3.2.26)
The corresponding eigenvector is
o(_)(p, k) = A 1, l[Vl,(k)-- V22(k)] + x / { l [ v , l ( k ) - V22(k)]}2 + [ V,z(k)l; (3.2.27)

where A is the normalization constant determined by the normalization condition
2
Z I°(-)(P,k)l 2= 1
p=l
As was shown in Section 2.2, it follows from the maximal amplitude principle that the most
stable superstructures do not include nondominant waves. The latter condition can be met
when wave vectors of dominant waves generating the superstructure may be represented as
k0 = (000),H/2, H/3 or H/4 (3.2.28)
(see Section 2.4) All possible vectors/Co of the type of (3.2.28) being reduced into the first
Brillouin zone of the bcc lattice form the following finite sequence of stars:
~0 = (000), {lO0}, {½10}, "fl-l--l'l"
t : : 2 j , { ~110 } , { i 010 } , { ~ 0 0 } , { i i 011} and {22~} (3.2.29)
The structure of the stable secondary phase may be found within the same four neighbor
interaction model (3.1.1). Substituting the elements (3.1.3) of the matrix Vpq(k) into eq.
(3.2.26) and (3.2.27), we have
2(_)(k) = 8W3 cos rtk~ cos uky cos nk~ + 2 W4(cos 2rck~ + cos 2uky + cos 2rck~)
-12WLcosrck~+4W2cosr~kxcosrckyl (3.2.30)
and
_}.~( [ 2 W 1 COS nkz+4Wz cos nkx cos 7zky]e-in(kx -kY)_l (3.2.31)

V(_)(p, k) = 1,-- [2WlCOSrckz+4W2cosnkxcoszckyI
As shown in Section 2.2, the stable secondary superstructure is generated by the dominant
wave, its wave vector being chosen from the series (3.2.29) so as to obtain a minimum of the
spectrum (3.2.30). Since
WI >>W2 > W3 > W4 > O
(see the inequality (3.1.1)), the function 2(_)(k) given by eq. (3.2.30) assumes its minimum
value at
k~ = (kxkyO) or k~ = (kxkyl) (3.2.32)
The constraints (3.2.32) imposed on the wave vectors (3.2.29) enable us to eliminate some
of the wave vectors. The remaining wave vectors from the series (3.2.29) meeting the
conditions (3.2.32) form a reduced series:
k = (000), (100), (001), (½½0), (¼10), (½0 0), (2 0 0), (½½0) (3.2.33)
Substituting the wave vectors (3.2.33) into eq. (3.2.30), one may see that
,~(_)(k~½°°)) > ~t_)(k~½½°)); ~(_)(k~°°'~) > ,Z(_)(kp°°)); ~(_)(t,~½½°~) > ~(_)(t,~ °°))
In other words, the wave vectors k~½°°) (½ 0 0), kt °°~)= (001) and k tk½°)
1 ---\33
t! ! 0~1 also should
be excluded from (3.2.33).
The eigenvalues associated with the remaining wave vectors can be obtained by substitution
of the remaining wave vectors into eq. (3.2.30):
)~(_)(0) = --2W 1 - 4(W2 -- 2/4"3) + 4W4

2(_)(kt ~°°)) = -2W~ + 4(/412 - 2W3) + 4W4
~.t_)(k~½½°))= -2W~ - 2W 4
2t_)(k~~¼°)) = -2/411 - 2(W2 - 2/4"3) + 214"4
( - - )tb(]00)a
\~ 1 I -_- -2W~ + 2(W2 - 2W3) + 3W4. (3.2.34)
Comparison of the eigenvalues in (3.2.34) shows that the minimum eigenvalue may only be
realized at k~ = (000), k~ = (100) and k~ = (½½0). Fig. 7 shows a diagram in the variables W4
J.P.M.S. 29/I-2--D
to)
L
FIG. 7. Diagram of stability fields of secondary superstructures generated by the vectors k~ = (000),
kl = (g115 0) and k~ = (1 0 0) for the four neighbor interaction model.
and W2 - 2 W3 where the stability fields of the secondary superstructures associated with these
three wave vectors are indicated.
It follows from Fig. 7 that the minimum of the eigenvalues 2~_)(k) is attained at kl = (000)
if
1412--21413-- ~ W 4 ~ 0 , (3.2.35a)
at kl = (100) if
W 2 - 2 W3 + ~ W4 <~O (3.2.35b)
and at k I -- ( ~110 ) if
- W4 <~ W2 - 2 W3 <~~ W4 (3.2.35c)
To particularize this diagram, let us consider the more or less realistic pairwise repulsive
potential for interstitial atoms. Let the dependence of interaction energies on separation
distance between interacting interstitial atom pairs be described by the screened Coulomb
potential:
e2
Wi = - - exp( -- ri/ro) (3.2.36)
ri
where e is the effective charge on interstitial atoms, ri the separation distance, and r D the
Debye radius. The dependence (3.2.36) provides a good interpolation between both limiting
cases, the short-range interaction and the long-range Coulomb interaction.
Substituting the potential (3.2.36) into (3.2.35a, b, c) at r2 = a/x/~, r3 = av/3/2 and r4 = a
shows that:
(i) the inequality (3.2.35a) holds in the case of strong screening when
r D ~< 0.2036a. (3.2.37a)
In this case the minimum eigenvalue is attained at k = (000);
(ii) the inequality (3.2.35c) holds at

0.2036a < rD < oo (3.2.37b)
when the minimum eigenvalue falls on kl = (½½0).
Note that the screened Coulomb potential (3.2.36) cannot make the inequality (3.2.35b)
hold, which is required for the case k~ = (100).
The inequalities (3.2.37) show that the short-range interaction results in a situation when
the 2~_)(k) minimum falls on k~ = (000), whereas the long-range interaction close to the
Coulomb potential yields the minimum of 2(_)(k) on kl = (1½0).
To provide the minimum of 2(_)(k) at k, = (100), a quite unrealistic interaction model
should be assumed in which the potential decays with distance even slower than the Coulomb
potential. For example, the 2(_)(k) minimum would fall on kl = (100) if W~ is a constant, i.e.
does not depend on the separation distance at all. This means that the case k~ = (100) can
hardly be realized within a more or less realistic model. For this reason it will not be
considered below.
The secondary stable superstructure associated with the wave vector k~ = (000) is generated
by the dominant wave
v(_)(p, 0) = (v(_)(l, 0), v(_)(2, 0)) = ~ (1, I) (3.2.38)

, t ¢
which may be obtained by substituting k = 0 into eq. (3.2.31). The corresponding super-
structure generated by the dominant wave (3.2.38 is described by the distribution (2.3.1):
c 0 1
c 2 +7(-)()~ if p = l
n(o2)(p, R) = ~ + 7(_)(0)D(_)(p, 0) = v- (3.2.39)
c 1
- ~ - ~'(_)(0)-- if P = 2.
It should be remembered that the third Oz sublattice is by definition vacant, (n(025(3, R) = 0)

because it is forbidden in the primary "predecessor" superstructure described by eq. (3.2.23).
That is why the number of sublattices, v, in eq. (2.3.1) is equal to 2. Equation (3.2.39) assumes
either of the two values, 0 or 1, if ?(_)(0) = 1/x/~ and c = cst = 1. In this case
{10 if P = I
n(o2)(p, R) = if p = 2
or
n(02)(1, R) = 1 n~2)(2,R) = 0 n~2)(3,R) = 0. (3.2.40).

The distribution (3.2.40) coincides with the distribution (3.2.22) (to within the choice of
the tetragonal axis direction). It describes the situation when all O~ interstices (p = 1)
occupied by interstitial atoms and Oy and O~ interstices are vacant. As was mentioned above,
such a superstructure cannot be stable in the case of oxides because the strong tetragonal
distortion results in the bcc--, fcc host lattice rearrangement. It yields the NaCl-type
fcc-based structure (see Fig. 6). Therefore, in the case of the short-range potential (see eqs
(3.2.35a) and (3.2.37a) we arrive at the same conclusion as above: the NaCl-type structure
should be formed. This structure may, however, be formed only for a divalent metal oxides
and is really observed for most of divalent metal oxides. If the valency of metal atoms is more
than 2, we will have the same NaCI structure but with metal atom vacancies. Tertiary ordering
of these vacancies will, however, occur over octahedral sites of the fcc host lattice rather than
the bcc host lattice. This case will not, however, be discussed in this Chapter since we consider
here only superstructures based on the bcc host lattice.
The secondary superstructure associated with the wave vector kl = (i~ iT 0) is generated by
the dominant wave*
o(_)(p, k~½~°))exp(i2nk~½~°)R) (3.2.41)
whose "polarization vector"
- ,T , I'~ 1.('~-oh~
o(_)(p, k~½½°))= (o(_)(1, k~°)), ~'(-)',', ~I jj = (1, 1) (3.2.42)
may be obtained substituting

k~½½0)= ½a~ lT
- - iI a 2, = (~iO) (3.2.43)
(a*, a* and a~' are the unit reciprocal lattice translations along the [100], [010] and [001]
direction; I a* I = I a* I = I a* I = ~) to eq. (3.2.31). Making use of (3.2.42), (3.2.7) and
(3.2.43) in eq. (3.2.41) we have
ii ~i l
v(_)(p, k} 22°)) exp (i2nk~°)R) = ~ (1, 1) exp (in(x - y)). (3.2.44)
The distribution n~2)(p, R) describing the secondary superstructure is generated by the

dominant wave (3.2.44) in compliance with eq. (2.3.1):
n~2)(p, R) = ~c + y(_)(k,(iio). 1
22 )-~_ (1, 1) ei"(x-y)
x/z
- + ?(-) (k (1~ ° ) )x/~

- e *n(x-y) if p = l ( 0 x sublattice)
= f~ 1i 1 . (3.2.45)
c ~ ,, t,(½~0
"~ r ¥ ( _ ) n 1 h1 ~ 1 ein(x_y) if p = 2 (Oy sublattice)
To make the function (3.2.45) to be equal either to 1 or to O, we should assume that c = cst = 1
~T 1
and y(_)(k~~°)) = ~ . In this case
~'1/2 +½exp(in(x - y ) ) if p = 1 (3.2.46a)

n~2)(p'R)= [1/2+½exp(in(x y)) if p = 2
or
n~2)(1,R)=n~2)(2, R ) = l/2 + l exp(in(x - y)), n~2)(3,R ) = 0 (3.2.46b)
Placing metal atoms, M, into octahedral interstices of the Ox and Oy sublattices where
n~2)(p, R ) = 1 we obtain the secondary superstructure of Fig. 8(a). Since the constant term
in eq. (3.2.46) which determines the fraction of Ox and Oy occupied by M atoms is equal to
1/2, we have the following stoichiometric formula
[M1/2 I--ql/2][M1/2 I--]~/2]O = MO. (3.2.47)
ii li
*The k~ 22°)= ( ~iT 0) vector is equivalent to the ~22o) = ( ~I 1 0) vector. The former is, however, more convenient
since it simplifies the theoretical analysis.
The formulae within the first and second brackets in eq. (3.2.47) characterize the ratios
between interstitial M atoms and their vacancies, [:], in Ox and Oy sublattices, respectively;
O designates oxygen atoms.
The stoichiometric secondary superstructure, MO may be, as shown in Fig. 8(a), formed
in the case of divalent oxides. Note, however, that this structure was not really observed in
this form. The reason is the same as with the MO superstructure displayed in Fig. 5(a), viz.
the bcc host lattice becomes unstable with respect to host (oxygen) atom displacements
induced by interstitial metal atoms.
3.2.1. Host lattice instability produced by secondary ordering (3.2.46)

As was mentioned above, the same occupation of the Ox and Oy sublattices results in the
same homogeneous extension of the bcc host lattice along the [100]~ and [010]~ axes and,
therefore, Poisson compression along the [001]~ axis. Such a homogeneous tetragonal strain
applied to the bcc host lattice produces a body centered tetragonal (bet) lattice with the
_J..
I I 4 A
" L
,ll
(~) ~
TX"_ ;;'Y [oo~]k,
/ /s~-CY--/-"
d .t * 4
FiG 8 (a) The M e secondary superstructure generated in O~ and Oy octahedral interstices by the
vector km= ( ~iT 0) in accordance with the distribution function (3.2.46). O, Oxygen atom; 0 , metal
atom. Dash lines indicate planes in the bcc host lattice normal to [1T0]~. (b) The NiAs-type structure
formed from the bee-based M e interstitial superstructure (a) by means of [110l (IT0) host lattice
shuffling induced by interstitial atom ordering. O, Oxygen atom; Q, metal atom. Arrows indicate the
direction of O atom shuffling produced by interstitial atoms. The horizontal hatching shows the
component of the (001) plane of the primitive hexagonal lattice formed by interstitial metal atoms.
Small open circles indicate O z vacant interstices.
54 PROGRESS IN M A T E R I A L S SCIENCE
tetragonal axis directed along the [001]~ axis and the tetragonal ratio c/a < 1. Besides the
homogeneous tetragonal strain, heterogeneous ordered distribution of interstitial M atoms
in the secondary superstructure presented in Fig. 8(a) results in heterogeneous host atom
displacements from bct host lattice sites.
The amplitude of the static displacement wave generated by the dominant concentration
wave of the superstructure is determined by eq. (2.7.15). Substituting (2.7.12) and (3.2.42) to
(2.7.15), we have
w(kl)=y(_)(kl) ~=1 m~2---~l)

e~'(kO pz'~£'-1- (F°ct (p' k,) e~(kl)*)v(_)(p, kl) (3.2.48)
where k~ = (~|T~ 0), e~(kl) is the polarization vector of the ~t-th vibration mode. At kl = (~17~ O)
there are the following polarization vectors
e,(kO = ~/~ 0 , e2(k0 =

(-55) , ,0 , e3(k,) = (0, 0, 1)
corresponding to the longitudinal mode frequency, o92(kt), and two transversal mode
(3.2.49)
frequencies, ¢o2(kl) and_ o~3(kl), respectively.

Substituting k~ = (½½0) into eq. (2.7.24) for Foct(1,~¢k) and Fo~t(2,b¢¢k), we have
Foot ( 1 , / 1 ) ~---=-ta exp - - l ~ (0"33, --0"11, 0)
Foot(2, kl) = - i a 2 e x p z-~ (0"11,--0"33,0). (3.2.50)
Utilizing (3.2.42) and (3.2.50), we have

p=2 bcc b¢¢ 1 - -1
Foct(P,kl)O(-)(P, kl) = Foct(1, kl)]--/~ + eobcc,(2,
P 1 %,
,/~, 0 = --a2(0"33 -- 0"11)e2(/1) (3.2.51)
Using eq. (3.2.51) and the value 7(_)(kO = 1/x/~ following from (3.2.45) and (3.2.46) in eq.
(3.2.48), we obtain
a2(0"33- 0"11) a2(0-33- 0-11) (. 1 , 1 )
w(k0= mo922(kO e2(kt)= mog~(kl) \x/~ x//~, O/ (3.2.52)
where kl = (½~0).
The static displacement wave whose amplitude is described by eq. (3.2.52) results in
heterogeneous displacements of oxygen host atoms:
a2(0-33--0-11) i•(x )t/ 1 1 "~

u(R) = W(kl) exp(i2rck~R) = -m--~2~ e -y x\ x/ /2-~-,
21 . -=, 0/,/ (3.2.53)
Although the linear approximation is rough, the result (3.2.53) according to which the
displacement direction is parallel to the symmetry direction [I 10]~c proves to be also valid
in a more realistic model. In fact, this result is attributable to the symmetry of the problem
rather than to the concrete dynamics of interatomic interactions. That is why any refinement
of the model may change the magnitude of the displacement amplitude, w(kO, but cannot
affect the displacement direction.
Therefore, it follows from eq. (3.2.53) that every second (1T0)~ plane of the host lattice
in the structure depicted in Fig. 8(a) slides by the value 2a2(tr33- triO/mob(k1): with respect
to the nearest (1T0)~c host lattice planes along the [110]b~cdirection (i.e. along the polarization
vector, e2(kl) = (1/x~, 1/x/~, 0)).
Consequently, we arrive at the conclusion that interstitial metal atoms in the secondary
superstructure (Fig. 8(a)) produce two effects:
(i) the homogeneous tetragonal strain resulting in the bcc ~ bct host lattice trans-
formation with the axial ratio c/a < 1;
(ii) shuffling of the (1T0)b~ planes along the [110]b~ direction.
3.2.2. Formation of the NiAs type structure

We go into such detail of the displacement problem because, as will be seen below, that
is the tetragonal distortion combined with the [110] (1T0)b~cshuffling that results in the host
lattice instability, diffusionless bcc ~ hcp host lattice rearrangement. Actually, if the axial c/a
ratio reaches its critical value c/a = x / ~ ~ 0.816, and the displacement of every second
(1T0)~ plane along the [110]~ direction becomes equal to 1/12 of the unit translation along
the [110]b~cdirection, the bcc host lattice becomes the hcp one, and the structure depicted in
Fig. 8(a) is transformed into a NiAs-type structure (B8~, P63/mmc)328~ The crystal lattice
correspondence between the initial bcc-based superstructure and the resulting hcp-based
NiAs-type superstructure is displayed in Fig. 8(b). It follows from Fig. 8(b) that the
orthorhombic sublattice composed of Ox and Oy interstices undergoes at the bcc ~ hcp
transformation homogeneous deformation only, its principal axes running along the [110]b~,
[001]~c and [1T0]b~c directions, i.e. along the basic unit cell vectors of the orthorhombic
sublattice. Such a deformation does not produce any displacements of interstitial metal atoms
from the corresponding sites of the orthorhombic sublattice of octahedral interstices. In other
words, the mutual disposition of metal atoms is not affected by the bcc ~ hcp transformation
to within the homogeneous deformation. As for the host lattice, it undergoes both
homogeneous deformation and heterogeneous [110](1T0) shuffling.
Therefore, at equal valencies of both constituents, metal and metalloid, at large static
displacements (this certainly is the case with a nonmetal equatomic compound) and at
corresponding relation between interaction energies, the formation of the hcp-based NiAs-
type structure becomes inevitable.
It is of interest to note that the NiAs-type structure is not observed in the case of oxides
which is discussed here, but it is however widely observed for binary chalcogenides, FeS, NiS,
CoS, NiSe, CoSe, MgTe, NiAs etc. (29-3°)The reason for this is not quite clear yet. It is possible
that this fact might be associated with the atomic size of host atoms. Chalcogen atoms S,
Se, Te and As, have considerably larger atomic diameters than oxygen atoms and thus the
host lattice parameters in chalcogenides should be considerably larger than in oxides. In
effect, this means that the separation distances between interstitial atom pairs in chalcogenides
are larger than in oxides, which, of course, affects the relation between interaction energies,
w,.
3.2.3. Tertiary ordering resulting in the rutile structure

Returning to titanium oxides, one may notice that the Ti/O ratio for the secondary
superstructure of Fig. 8(a) falls beyond the range of Ti/O stoichiometries (3.2.1). For that
reason, some Ti atoms should again be removed, and the resulting nonstoichiometric
vacancies should be tertiary ordered over the "permitted" interstices {p, r} of the secondary
superstructure so as to provide a maximum reduction of the configurational energy.
According to the theoretical concepts formulated in Section 2.8, the energy change caused
by the tertiary ordering is determined by the m a t r i x [~pq(k). This matrix is defined by the
equation
~pq(k ) = E Wpq(r) e -~2nk" (3.2.54)
r
where the summation is carried out over reference vectors, r, labelling the "permitted"
interstices {p, r}. Equation (3.2.54) holds if the reference vectors {r} form a Bravais lattice.
This is just the case with the parent secondary superstructure of Fig. 8(a). Since, by the
definition of "permitted" and "forbidden" interstices, n~2)(p,R)= 1 at R = r and
n~2) (p, R) = 0 at R ~ r, we may extend summing in eq. (3.2.54) to all bcc sites, R, introducing
the "weight" factor, n~2) (p, R) in eq. (3.2.54):
~pq(k ) = ~ Wpq(R )nt2)(p, R ) e -i2~kR. (3.2.55)

R
Substitution of eq. (3.2.46) to (3.2.55) yields
~pq(k) = ½[V,q(k) + Vpq(k - k0] (3.2.56)
iT
where kl = (~ i 0).
Making use of eq. (3.1.3) in (3.2.56), we obtain
~'pq(k)~_~ pll(k) ~12(k)~
V2 (k)]
where
P . ( k ) = ~22(k) = 4W3 cos ~(kx + ky) cos ~k~ + 2W~ cos 2~k~
l~12(k) = 21412cos ~(k~ - Icy) exp(i~(kx - ky) ). (3.2.57)
The lower branch of eigenvalues of the matrix (3.2.57) is
~(_)(k) = ~ll(k) - [ ~12(k) [ -~" 4W3 cos n(kx + ky) cosrck~
+ 214/4 cos 2rck~ - 2W2 [cos ~(k. - ky) [. (3.2.58)
The corresponding elgenvector is
1 ( 1, 'l~2(k)*
~<_)(p, k) = (e<_)(1, k), ~<_)(2, k)) = f-~ )I~,2(k)[
~d
- 1, - I cos ~ ( k ~ - k,)l e
As was shown in Section 2.4, the wave vector of the dominant waves generating the
superstructure meeting the maximum amplitude principle has the form:
k2 = H/Sl (3.2.60)
where s I --- 2, 3, 4. In the above case of tertiary ordering, H are reciprocal lattice vectors of
the parent secondary superstructure described by eq. (3.2.46). It includes both fundamental
reciprocal lattice vectors, H ~ , of the bcc host lattice and superlattice reciprocal lattice vectors,
_ti
H = k~22°) + Hb~c
C H A R A C T E R I Z A T I O N OF CERAMIC CRYSTALS 57
of the parent secondary superstructure depicted in Fig. 8 (b). Being reduced into the first
Brillouin zone of the parent secondary superstructure, the wave vectors (3.2.60) form a finite
series. The analysis of the values assumed by ;[(_)(k) (it is given by eq. (3.2.58)) with wave
vectors of this series shows that the minimum eigenvalue, - 214"2- 4W3 + 2W4, is attained
at
k r = k ~ ½½°)-
- ( ~110 ) (3.2.61)
In compliance with eq. (3.2.59), the eigenvector corresponding to the wave vector
k = kr (½10) is
=
~(_)(p, k,) = ~ (1, T) (3.2.62)
and therefore the dominant wave itself is

1
~(_)(p, kr)exp(i2nkp) = --~ (1, T)exp(i2nkrr) (3.2.63)
The dominant wave (3.2.63) generates the tertiary ordered distribution which may be
obtained by substituting eq. (3.2.63) into (2.3.1)
nl3)(p, r) = c + 7<-)(k,)o<-)(P, kr) e a"kr"
+7(_)(kr)--~exp(i2rckr r) if p = 1
= (3.2.64)
1
-- 7(_)(k~) ~ exp(i2rckrr) if p = 2
Since exp(i2nkrr) can only be either + 1 or - 1 on reference vectors, {r}, related to the
"permitted" interstices of the parent secondary superstructure, the function n ~3)(p, r) is 0 and
1 only if c = 1/2 and Y~-)(kr) = 1/x/~. Then
S½+½exp(i2~kr r) if p = 1 (3.2.65)
nt3)(p'r) = ~½-½exp(i2nkrr) if p = 2
To rewrite the distribution (3.2.65) in terms of arbitrary bcc host lattice sites, {R}, i.e. to
introduce the host lattice sites, {R}, instead of the "permitted" parent secondary super-
structure sites, {r}, eq. (3.2.65) should be transformed into
n3(p,R)=n~2)(p,R)n~3)(p,R)=(n~3)(p,r) if R = r (3.2.66)
o if R :A r
Equation (3.2.66) holds because, by definition, the function n~:)(p, R) is equal to unity on the
"permitted" parent secondary superstructure sites when R -- r, and equal to zero on all the
other "forbidden" sites when R :~ r. The substitution of (3.2.65) and (3.2.46) into (3.2.66)
yields:
i i i_r
f 1 I ,2,kl~°°~R+~l [e,~o,R + ea~kl~o,R] if p = 1

n3tp, R ) = ~ + ~ e ,, ,~
l~-~e~ +~ [-- e '~"kg~°'R+ e a~k~°'~] if p = 2
~ ~2"kl~°°~R~ (3.2.67)
Substituting k] 1°°)= 23*, k, = (a* + a*), k] ½½°)= a? - a*, and R = xal + ya2 + za3 to (3.2.67),
we have
1 1 z2nx 1 [ein(x + y) ..~ ei~(x - y)] if p 1
n 3 ( p , R ) = J'Z
~1 + Z 1 e f2rcx + ~
1
= (3.2.68)
( ~ -- ~ e + ~ [ - - e"~x + Y) -k- e ~'~x - y)]
"
if p = 2
FIG. 9. The tertiary bcc-based interstitial superstructure MO2 generated by the distribution (3.2.68).
Atomic positions coincide with those of the rutile structure, TiO 2. O, oxygen; O, metal atom.
Injecting Ti atoms into Ox and Oy interstices, {p, R} = {p, x, y, z), of the oxygen-based bcc
host lattice in which the n3(p, R) function given by (3.2.68) is equal to unity and keeping the
other octahedral interstices vacant, we obtain the atomic structure shown in Fig. 9. This
structure corresponds to the stoichiometric formula
(Til/4 [--]3/4)(Til/4 [~3/4) O = Ti~/20 or TiO 2
The Ti/O ratio equal to 1/2 is within the range of stoichiometries (3.2.1) and corresponds
to the Ti valency state 4- 4. The structure TiO2 which we have determined is thus the stablest
structure of a titanium oxide with the Ti valency equal to +4.
It is worthy of note that the theoretically predicted atomic arrangement shown in Fig. 9
is actually realized to within small displacements caused by ordered distribution of interstitial
Ti atoms and corresponds to the rutile structurefl ~)The rutile structure is the most widespread
oxide structure based on the bec host lattice, composed of oxygen atoms. Examples are TiO2,
VO 2, CrO2, MnO2, SiO2-stishevite, TaO2, RuO 2, AsO 2, GeO2, SnO 2, PbO2, InO2 and slightly
distorted rutile structures, WO2, MOO2, TeO2, RuO2.(3DThe rutile structure is also observed
in metal fluorides such as MgF2, MnF2, FeF 2, CoF2, NiF 2, PdF2, ZnF2 .~32)
Finally, let us note the orientation relations between the rutile lattice which is a tertiary
superstructure and the bcc host lattice. It follows from Fig. 9 that
[100]rutile//[110]b~c, [010]futile//[1T0]bcc,[001]rutilJ/[001]bcc
The relation between the rutile reflection indicies and those indices related to the bcc crystal
reciprocal lattice is the following:
(H~t)x = ½ [(H~)~ - (HbJj:]
(H~..t)y= ½ [(H~¢)x + (H~¢)y]
(H,~t),= iI (Hb~).,.
3.3. Alternatives to the Rutile Structure: the ~t-PbO: and Corundum Structures
As was shown within the framework of the simple short-range interaction model in Section
3.2, that the rutile structure, TiO2, has the lowest configurational energy and therefore is most
stable at Ti valency equal to 4- 4. One should, however, bear in mind that this model is rather
rough and should be considered as the first approximation to the theory. Refinement of the
model such as taking into consideration long-range interatomic interaction may, in principle,
change the conclusions of the theory in favour of other alternative structures.
It follows from the foregoing that the configurational energy of any structure calculated
within the framework of the short-range interaction model (3.1.1.) exceeds the rutile structure
energy. This simple model enables us, however, to find a structure alternative to the rutile
one. Indeed, the model configurational energy should be only slightly higher than the ground
state energy corresponding to the rutile structure. In other words, the energy gap between
the alternative and rutile structures shoud be minimal, for otherwise, if the energy gap is large,
it would hardly be probable for slight long-range interaction to outbalance this energy gap
and thus to make the alternative structure more stable. Therefore, we come to a rather simple
procedure for the determination of the alternative phase structure without extension of the
simple short-range interaction model. The latter is of utmost importance because, as a rule,
we lack information needed for refinement of the short-range interaction.
The structure determination procedure for the alternative phase consists of the following:
(1) constructing all the tertiary superstructures meeting the maximum amplitude principle;
(2) arraying the resultant superstructures in an increasing order of energies calculated
within the frame of the short-range interaction model (3.1.1) (the ground state structure of
rutile is the first one in the series thus obtained);
(3) choosing alternative structure from those which closely follow rutile in the series.
This procedure will be described in detail below.
Since the rutile structure is a tertiary superstructure, to determine the alternative
compound, we must return to the tertiary ordering based on the parent secondary
superstructure depicted in Fig. 8(a).
As mentioned in Section 2.3., the condition of the maximal amplitude is met in the case
of a layer structure described by eq. (2.3.1), i.e. generated by the only "polarization" of the
dominant concentration wave. To see when this condition can be met, we will take advantage
of the fact that the function, n (p, r) describing a completely ordered distribution of interstitial
atoms in a tertiary superstructure remains unaffected by raising it to any power;
(n(p, r ) y - n(p, r) (3.3.1)
since n(p, r) can be either 0 or 1.

Substituting eq. (2.3.1) into (3.3.1) and assuming s -- sl + l, one may readily see that the
identity (3.3. l) holds only in the case when raising the dominant wave, f(_)(p, k2) exp(i2nk2r),
generating the tertiary superstructure to a power sl + 1 gives the same wave, i.e.
(t?(_)(p, k 2 ) exp(i27~kEr)) sl + 1 = tT(_)(p, k 2 ) sl + 1 exp(i27rHr)

x exp(i2nk2 r) = flf(_)(p, k2) exp(i27rk2r ) (3.3.2)
where fl is a dimensionless constant.

In the derivation of eq. (3.3.2) the definition,
slk2 = H, (3.3.3)
following from (2.3.3) and thus the identity,
exp( i 27rslk2r ) - exp( i 2nHr ),
was taken into account. Since, by the definition of a reciprocal lattice vector H of the parent
secondary superstructure,
exp(i27~Hr) = 1,
eq. (3.3.2) may be rewritten as*
(tT(_)(p, k2) exp(i2nk2r))sl + ~= tT(_)(p, k2)S~+ 1 exp(i2nk2r ) = flf(_)(p, k2 ) exp(i2rck2r). (3.3.4)
The identity (3.3.4) is realized if
(f(-)(P, k2))s~+~ - flf~_)(p, k2) (3.3.5)

Using eq. (3.2.59) for v~_)(p, k ) , we find that the identity (3.3.5) holds if
~12(k2)*
( i ,12(k2) 1) " ' = l ' (3.3.6)
Substituting (3.2.59) into (3.3.6), we obtain
[-I e-in(kzx-k2yllS~=I _ ]cosTt(k2x_k2y)lC°sg(k2x-k2y)T'exp(-ilz(Hx-Hy))=l(3.3.7)

n(k2xC°Srr(k2x-k2Y)k2y)l
cos
where
Hx - 1-% = - k2y).
In summing up the foregoing, we may see that the maximum amplitude principle is provided
not for any layer superstructures but for the specific one whose vector, H = s~k2, character-
izing the alternation of filled and vacant planes meets the condition (3.3.7). As we will see
below, this condition substantially reduces the number of possible dominant waves.
It was shown in the end of Section 3.2 that the minimum of the function ;[(_)(k) given by
eq. (3.2.58) falls on k = k 2 = k , = ( ½ ½ 0 ) . This is what determines the dominant wave
generating the rutile structure. Refinement of the short-range interaction model (3.1.1) by
recognition of long-range interatomic interaction and corrections of short-range interaction
constants, W~, may, in principle, shift the location of the function ~_)(k) minimum from the
point k, to a neighboring point k2. The shift is determined by the relation
= k2 - kr. (3.3.8a)
The shift vector z cannot assume arbitrary values. By definition, it finds itself within the first
Brillouin zone of the parent secondary superstructure. The second constraint imposed on the
vector x follows from the maximum amplitude principle. To be specific, let us note that not
any wave vector k2 can be suitable to be a wave vector of the dominant concentration wave
generating the tertiary superstructure. In particularly, the wave vector kz and thus the shift
vector z should meet eq. (3.3.7) which follows from the maximum amplitude principle.
Using eq. (3.3.3) in (3.3.8a), we obtain
H - s]kr
= H / s l - kr - - - (3.3.8b)
$1
exp(i27~k2r
) to power s~ + 1 yields the same function.
*Choice o f the exponent in eq. (3.3.1) in the form s = s~ + 1 was justified by the fact that raising the function
3.3.1. Even numbers o f sl

Let us take up the case when s~ is an even number. The numerator in the right-hand side
of eq. (3.3.8b) is then a reciprocal lattice vector, H ' , of the parent superstructure:
H ' = H - slk, (3.3.9)
because k r = (511~ 0) and s~ is an even integer. Let us note that the vector k~ = ( ~110 ) as well
as any other vector, H = H ~ + k~, differing from it by a fundamental reciprocal lattice vector,
H ~ , of the bcc host lattice is, by definition, the superlattice reciprocal lattice vector of the
parent superstructure. It thus follows from (3.3.8) and (3.3.9) that
z = H'/Sl. (3.3.10)
As shown in Section 2.4, the maximal concentration wave amplitude is attained when s~
is equal to 2, 3 or 4. This is just the case when structures with fixed stoichiometry are formed.
As we analyze the even values of Sl, the cases s~ = 2 and 51 = 4 should be considered.
Substitution of (3.3.10) into (3.3.8a) yields
k 2 = k r + z = k r d- H ' / s t . (3.3.11)
Making use of (3.3.11) in (3.3.7) and assuming s~ to be an even integer, we may rewrite
eq. (3.3.7) as
l
exp(-- irc(H'x -- Hy)) = 1. (3.3.12)
The constraint (3.3.12) imposed on the reciprocal lattice vector H ' of the parent super-
structure results in the following condition:
H'x-H'y=21 where 1=0,+1,+2,+3 .... (3.3.13)
Since the shift vector z = H ' / s , is confined by the first Brillouin zone, and Sl is equal to either
2 or 4, the reciprocal lattice vector, H', proves to be also confined. Taking this constraint
and (3.3.13) into account, we have the following finite series of suitable H ' vectors:
H ' = ( ½ ½ 1),(110), (110), (23-~1),(002),(112) at s~ = 4 (3.3.14a)

H'=(Ii11 1) at s1=2 (3.3.14b)
[the half-integer indices in the series (3.3.14) are referred to the superlattice reciprocal lattice
vectors, H ' = kl + H~¢c= (½~ 0) + H ~ , of the parent secondary superstructure]. It was noted
in the beginning of this section that the energy gap between the alternative structure and the
ground state rutile structure calculated within the framework of the short-range interaction
model (3.1.1) should be minimal. Therefore, the eigenvalue
~ _ ) ( k 9 = :~_ >(k, + ~)
corresponding to the alternative structure should assume the minimal value at z # 0 (the case
of • = 0 corresponds to the ground state rutile structure and provides the absolute minimum
of ~[(_)(k, + z)). Substituting k2 = kr + "c given by eq. (3.3.11) into eq. (3.2.58) yields
7g
~( _)(k r "~- H ' / s O = -- 2W2 [ cos - (H;, - Hy) l
s1
2~ ,
-4W3cosn--(H'x+ Hy)cos-Hz+ 2W4cos--Hz. (3.3.15)
SI S1 S1
To find the minimum value of ~[(_)(kr .-1-"C) at a nonzero 3, we must substitute the reciprocal
lattice vectors, H ' , and associated values, sl, into eq. (3.3.15) and compare the calculated
eigenvalues thus obtained. Comparison of all eigenvalues obtained by this way shows the
minimum eigenvalue at t # 0 to be
+ gH(½½1)) = - 2 W 2 - 2W 3.
It falls on H ' = (½ ½ 1) at sl = 4 for any relation between interaction constants, Wz, W3 and
W4, meeting the sole condition, W2 > W3 > Wa > 0. This eigenvalue immediately follows the
absolute minimum eigenvalue
~(_)(kr) : - 2 W 2 - 4 W 3 -1- 2 W 4
corresponding to k 2 = k r and related to the ground state rutile structure. Since the minimum
eigenvalue at z =/: 0 is provided by H ' = (½ ½ 1) and s I = 4, these values determine the wave
vector of the dominant concentration wave of the alternative tertiary superstructure
according to eq. (3.3.11). Substituting H ' = (½ ½ 1) and s~ = 4 to eq. (3.3.11) gives
k2 = kr +~H<½½,>
' ' (~½
' 0)+¼(½~' 1 )
= =
(~
Reducing the vector k2 = (~ ~ ¼) into the first Brillouin zone of the parent secondary
superstructure may be carried out by means of subtracting the reciprocal lattice vector
H = (½ ½ 1) of the parent superstructure from the relevant wave vector k2 = (~ ~5~).~.
k2=(~¼)-(½½ 1)=(~).
This brings us to the conclusion that the dominant wave generating the tertiary superstructure
alternative to the rutile structure has a wave vector
k2 = E11~) = ~H(H~). (3.3.16)
Equation (3.2.59) with k = k2 = ](11~;) gives
1
~(_)(p, k2) = ~ (1,I). (3.3.17)
Therefore the dominant wave generating the alternative superstructure is
~ _ )(p, k2) exp (i 2~zk2r ) = f ~ ( 1, T) exp (i 2~k2r) (3.3.18)

" V
where v are reference vectors of the bcc host lattice related to the {p, r } interstices "permitted"
in the parent superstructure shown in Fig. 8(a).
Equation (2.3.1) may then be rewritten in the form
n [3)(p, r) = c + 1[7<- )(k2)~<_ )(p, k2) exp (i27rk2v)
+ 7(- )(/2)*~(-)(P, k2)* exp ( - i2rck2r)] (3.3.19)
where
~), ~_)(p, k2) = (1, T)
To provide for the function (3.3.19) to assume only two values, either 0 or 1, we must make
in eq. (3.3.19) c =½ and
?( )(k2) = -~_ e in/4.
_
Equation (3.3.19) then reads
n~3)(p, r ) = i1+ ~--~

1 FLei~/4~ 1 (1, T) exp(i2nk2r ) + e -i~/4v~ - (1, I) exp(-i2nk2r)]
j'~ + ½[cos 2nk2r - sin 2r~k2r] if p = 1 (3.3.20)

= ~½- ½[cos 2r~k2r - sin 2nk2r] if p = 2.
To represent the distribution (3.3.20) as a function of arbitrary bcc lattice site vector R, eq.
(3.3.20) should be rewritten in the form similar to eq. (3.2.66):
n4(p, R) = n t2)(p, R )n ~3)(p,R) (3.3.21)
[~+-~exp(i~(x--y))]
1 1 Fl
L~ + ~l /~COS-~
Tt (x + y --6z)
-sln-~(x+y-6z) if p - - 1
n4(p, R) =
1 1
[~+~exp(#t(x_y))][l~ f n (x + y --6z)
/ ~ - ~ ~cos-~
--sln-~(x -t-y --6z) if p ----2 (3.3.22a)
since k2R = (~al

l , + ~a2
1 , -6a*)(xal+ya2+za3) = ~ ( x + y - 6 z ) .
Equation (3.3.22a) may be rewritten as
~+-~exp(irc(x-y))+ cos (x + y - 6 z ) - s i n ~ ( x + y-6z)
+~ cos~(5x-3),-6z)-sin (5x-3y-6z) if p = l
n4(p, X ) --
1 1 1[ n n ]
"~+ -~exp(in(x -- y)) -- ~ cos ~ (x + y -- 6z) -- sin ~ (x + y -- 6z)
4 cos ~ (5x - 3y - 6z) - sin

4 (5x - 3y - 6z)
1 if p -- 2 (3.3.22b)
where (x, y, z) are coordinates of the bee host lattice reference vector, R, n4 (3, R) = 0, by the
definition, of the parent superstructure.
Substituting the coordinates of bcc host lattice sites
(R(x,y, z) = (000), {½½½}, {100}, {~ ½½}, {110} . . . . )
into eq. (3.3.22b), one may readily see that the distribution function n4(p, R) can indeed be
either 0 or 1 over all octahedral interstices {p, R} of the bee host lattice.
Injecting interstitial atoms into the octahedral interstices of the bee host lattice on which
n4(p, R) is equal to unity and leaving vacant the interstices on which n4(p, R) is zero, we
obtain the tertiary superstructure alternative to the rutile structure. The atomic arrangement
shown in Fig. 10 describes the new polymorph of the TiO2 compound to within small
displacements of oxygen host atoms. This is the so-called ~-PbO2 structure frequently
occurring in oxides with formula MO2. (33,34)
The theory described above thus predicts the ~t-PbO2 structure as an alternative structure
to the rutile one. The ~-PbO 2 structure is, as a rule, more stable under high pressure whereas
the rutile structure is more stable under normal pressure conditions. For many synthetic
&
~ [tto]b
t I [ .L.-'l,," r .,F-J I/
' /1 ,I/i I~1 L:/I/ I

/I...4"I.L b. /
I,t'L/ ,
"1><1 1/.'1.-1 I /
ILL../ I
L./"-T-- J
FXG. 10. The alternative bcc-based MO 2 tertiary superstructure generated by the distribution
(3.3.22b). Positions of O atoms and metal atoms coincide with those of the e-PbO2 structure. For
simplicity O atoms composing the bcc host lattice are not shown. The nearest oxygen atoms are
displayed only for one of metal atoms. For the rest of metal atoms, nearest O atoms form the same
configuration. Heavy line indicates the unit cell of the superstructure.
mixed oxides and naturally occurring minerals (in particular, for columbites and tantalites)
both polymorphs are known; their transformations to each other are associated with small
variations of external thermodynamic parameters. (35)
Finally let us note that making use of eq. (2.6.3), one may see that the intracrystalline field
¢(R) induced by ordered distribution of Ti atoms in the rutile structure [see eq. (3.2.68)] on
the bcc host lattice sites occupied by O atoms is a constant value. This is evidenced by the
fact that each O atom in the rutile structure has the same atomic environment. In this situation
there is no reason for O atoms to undergo the heterogeneous displacements to equalize their
chemical potential. As for the homogeneous tetragonal strain produced by interstitial Ti
atoms, it does not violate constancy of the intracrystalline potential over oxygen atom sites.
Unlike the rutile structure, interstitial atoms in the ~-PbO2 structure produce a hetero-
geneous potential on the bcc host lattice sites occupied by O atoms. As follows from Fig.
10, there are two types of O atoms differing from each other by spatial location of
environmental atoms. This fact contradicts the requirement for O atoms to have the same
chemical potential which is the necessary condition for equilibrium. Nature "resolves" this
contradiction by means of heterogeneous displacements of O atoms to provide the same
atomic environment around each O atom. Since the ct-PbO2 structure is a completely ordered
tertiary phase based on the bcc host lattice, the orientational relations between the bcc lattice
and the ~-PbO2 structure may readily be found. It follows from Fig. 10 that the crystal lattice
correspondence between both structures are determined by the orientational relations:
1 1 0 ! 3
T T
2
3.3.2. O d d n u m b e r s o f s 1
We shall now consider the case o f o d d sl integers which m a y be written as
s~ = 2n - 1 where n t> 2 is an integer. (3.3.23)
E q u a t i o n (3.3.8b) m a y then be represented in the form
H H 2 H - 2(2n - l)kr
=---k,= - - k,= (3.3.24)
sl 2n - 1 2(2n - 1)
where H is the reciprocal lattice vector o f the parent superstructure described by eq. (3.2.46).
Let us introduce the f u n d a m e n t a l reciprocal lattice vectors, H,, o f the parent secondary
superstructure meeting the condition
½Hr = k r q- H (3.3.25)
T o within an a r b i t r a r y reciprocal lattice vector H o f the parent superstructure, the vector ½H,
coincides with the "rutile" point o f the reciprocal lattice k , = (½ ½ 0). E q u a t i o n (3.3.25) m a y
also be rewritten in the f o r m
H , = 2kr + 2 H (3.3.26)
Using the definition (3.3.26), we m a y express 2k, t h r o u g h H , and rewrite eq. (3.3.24):
H, - 2n (H, - 2H) H, - 2H'
= (3.3.27)
2(2n - 1) 2(2n - 1)
where H ' = n ( H , - 2 H ) is also a reciprocal lattice vector o f the parent secondary super-
structure. W i t h o u t loss o f generality, we m a y therefore use the substitution
Hr-2H'~H,
in the n u m e r a t o r o f (3.3.27). T h e substitution gives
H,
= (3.3.28)
2(2n - 1)
where H, is again a vector defined by the relation (3.3.26) so that • would be within the first
Brillouin zone of the parent superstructure. The list o f the H, vectors arrayed in order o f
increasing their absolute value is presented in Table 1. T h e vector, k2, is, by definition (3.3.8a),
separated f r o m the nearest reciprocal lattice "rutile" point, i/'/r, by a distance ~. The latter
c o m b i n e d with the definition (3.3.28) yields
1
k2 = ½H, + "c = ½Hr "4- H, (3.3.29a)
2(2n - 1)
Table 1. List of Reciprocal Lattice Vectors Hr in the bcc Host Lattice

Arranged in the Order of H, Vector Magnitude
N ° (H~xH,yH,~) N ° (H,xH~yH,~) N ° (H,xH.yH,.) N ° (H.,H.yH,,)
1 110 8 330 15 512 22 1T6
2 200 9 420 16 530 23 532
3 112 10 402 17 334 24 514
4 310 11 204 18 600 25 226
5 222 12 312 19 006 26 622
6 312 13 510 20 424 27 316
7 114 14 314 21 442 28 710
J.P.M.S. 2 9 / I - ~ E
or
n
k2 - - - Hr (3.3.29b)
2n - 1
Since 2k~ = 2(½ ½0 ) = (110), we have the relation
2(k~x - kry) = 0 (3.3.30)

which will be useful later.
The vectors H are, by definition, reciprocal lattice vectors of the parent superstructure.
They include both the fundamental reciprocal lattice vectors, Hec (they are reciprocal lattice
vectors of the bcc host lattice) and the superlattice reciprocal lattice vectors (they are defined
by the relation H--k~½½°)+ H b J . One may thus readily see the 2 H vectors to be always
reciprocal lattice vectors of the bcc host lattice. Since 2 H is a reciprocal lattice vector of the
bcc crystal and the difference between any two components of a reciprocal lattice vector of
the bcc crystal is an even number, the following condition holds:
2H~ - 2 H y = even number. (3.3.31)
Combining eqs (3.3.30) and (3.3.31) we, following eq. (3.3.26), have
H~x - Hry = even number. (3.3.32)
It follows from eq. (3.3.29b) and (3.3.23) that the difference H x - H y in eq. (3.3.7) is
n
H x - Hy = s~(k2~ - key) = (2n -- 1) ~ (Hrx - Hry) = n(Hrx - Hry) (3.3.33)
Substituting the relation (3.3.32) into eq. (3.3.33), we obtain

H x - Hy = Sl(k:~ - kEy) = even number. (3.3.34)
Equations (3.3.34) and (3.3.23) enable us to simplify the condition (3.3.7), rewriting it in the
form
cos zt(k2x - k2y) 1.
(3.3.35a)
I cos ~ (k2x - k2y) I
Using eq. (3.3.29b) and (3.3.29a) in (3.3.35a), we have
n
cos ~ ~ (H,x -- H,y)
= 1 (3.3.35b)
n
I cos ~ ~ (~/rx - ~ry) I
or
1
cos n 2(2n -- 1) (H,x - H~y)
cos ~7t (H ,x - Hry) = 1. (3.3.35c)
1
[ cos n 2(2n - 1) (Hrx - Hry) [
Condition (3.3.35b,c) and the relation (3.3.29b) strongly constrain the wave vector k2 of the
dominant concentration wave.
3.3.3. The case of sl = 3. The corundum structure

Among all odd values of s~ the value s~ --- 3 is of special importance. As shown in Sections
2.4 and 3.2, it is the value s~ = 3 that provides most complete fulfilment of the maximal
amplitude principle and thus may result in a high stability tertiary superstructure. In this case
the tertiary superstructure may be generated by the sole dominant concentration wave, and
has fixed stoichiometry.
If sl = 2n - 1 = 3, n = 2. By virtue of eq. (3.3.28)
= Hr/6. (3.3.36)
Equation (3.3.36) imposes a constraint on the magnitude of the Hr vectors, since the shift
vector • is, by definition, within the first Brillouin zone of the parent secondary super-
structure. Actually, the choice of too long vector H, would result in exit of • from the first
BriUouin zone. The latter fact together with the constraint (3.3.35b) at n = 2 sharply reduces
the number of suitable Hr vectors. In particular we may choose only three suitable Hr vectors
from Table 1 which lists them
H r = (200), (112) and (312) (3.3.37)
By virtue of (3.3.29b), the corresponding k2 vectors are
k2 =2(200),2(1T2) and 2(312) (3.3.38)
Substituting the vectors k2 from (3.3.38) into eq. (3.2.58) yields
-W2-2WH+2W at k2=(400)
~(_)(k2) =
f WE 2W3--W 4 at k 2 = ( 2 ] ~ )
WE + W3 -- W4 at k2 = (2 2 34_).
As follows from eq. (3.3.39), the lowest eigenvalue falls at
(3.3.39)
k 2 --/2~4-~
~,3 3 3J (3.3.40)
Substituting k2 = (2 ] 34_)into eq. (3.2.59) gives
°(-)(P, k2) = 1 (1, e-i4"/3). (3.3.41)
,/2
Therefore at sl = 3 the dominant wave providing the minimum of eigenvalue (3.2.58) is
?p(_ )(p, r) = (~(_)(1, k2), ~( _ 7(2, k2)) exp (i2nk2r)
= ~ 2 ( 1 , exp(-i4-~))exp(i2r~k2r) (3.3.42)
The distribution function (2.3.1) generated by the dominant wave (3.3.42) is

nt3)(p, r ) = c + l[7(_)(k2)~(_)(p, k2) exp(i27tk2r) + 7(_)(k2)*~(_)(p, k2)* exp(--i27tk2r)]
,[ ,
=
f x exp(-i27~kzr)l
-'1
J
if p = 2.
1 4
c + ~ 1 y{_7(k 2 ) ~1 e_i4~/3exp(i27rk2r) + T(_)(k2) , ~, / 2 ei n/3
(3.3.43)
Since k~ = (2 2_-
3 _4~
31 _- - !3 "1(214), the distribution function should have the form (2.4.6). This proves
to be possible if
7(_)(k0=
./5
2,, and c=-
2
3 3"
Equation (3.3.43) may then be rearranged
f l - 2 c ° s i rrk2r i f 3 ~ = l (3.3.44)
n~3)(p'r)= 2cos 2rrk2r--- if p = 2 .
Recall that the vector r in eq. (3.3.44) is referred to the reference vectors of "permitted"
interstices, {p,r}, of the parent superstructure. To express eq. (3.3.44) in terms of the
coordinates {p, R } = {p; x, y, z } of octahedral interstices of the initial bcc host lattice, we may
use the same procedure as in going from eq. (3.2.65) to (3.2.68), that is we should represent
the distribution function of the tertiary superstructure as the product
ns(p, R) = n~2)(p,R)n~3)(p,R) (3.3.45)
which automatically vanishes at "forbidden" interstices where n~2)(p,R ) = 0 by definition.
Substituting (3.3.44) and (3.2.45) into (3.3.45) yields
ns(p,R)=
~ [½+lexp(ilr(x - y ) ) ] [~ - ~2c o s - -4re
L [½+ ½exp(in(x
I ~ 42 r c 3
f (x - y +2z) 1 if p = 1
Y))] - c o s ~ ( x - y + 2 z - l )
1 if p = 2 (3.3.46)
since
k2R = ( gza , , --~a2
z , + ~a*)(xal + yazW za3)=2(x y +2z).
Equation (3.2.46) may be arranged as
l+le'~(~-Y)-~cos4~(x-y+2z)-~cos~(x-y-4z) if p = l
ns(p, R) = 4~z 1 rr
+½e i"(~-y) ½ c o s ~ ( x - - y + 2 z 1)-3cos-~(x-y-4z-4) if p = 2
ns(3, R) = 0 since n~2)(3,R ) - 0. (3.3.47)

In eq. (3.3.47), the identities
c o s 2 ~ (~x --gy
7 + ~z) - c o s ~(x
~ --y - 4 z ) ,
and
cos21r(7x -gY
7 +4 z - 32_)= c o s 3 ( x _ y - 4z - 4 )
were used. These follow from the relation

(~ ~ 3-) = (~ ~ :)3 + (1i2) where H~o = (1i2)
is the reciprocal lattice vector of the bcc host lattice.

t i'o]~,,
"x
FiG. 11. The bcc-based M203 tertiary superstructure generated by the distribution (3.3.47). Positions
of O atoms and M atoms coincide with those of the corundum structure A1203 up to small host atom
displacements caused by ordering of interstitial M atoms. O atoms composing the bcc host lattice are
not shown. Heavy line indicates the unit cell of the superstructure.
The first constant terms in eq. (3.3.47) equal to 1/3 indicate the fractions of occupied Ox
and Oy interstices in the bcc host lattice. The oxide formula may therefore be written as
[M1/3 R2/3][Ml/3 [-]2/3]0 = M2/30 (3.3.48)
or in the usual form M203.

In the case of titanium oxides this formula describes the Ti203 oxide. Its Ti/O ratio is equal
to 2/3 and thus is in the range of stoichiometries. The Ti203 oxide occurs at the trivalent state
of Ti atoms.*
Injecting Ti atoms into octahedral interstices, {p, R}, where the ns(p, R) function (3.3.47)
is equal to unity, we obtain the structure depicted in Fig. 11. Up to small displacements of
oxygen host atoms it coincides with the corundum structure ct-Al203, typical of the trivalent
metal oxides formed by elements of the first transition metal series/3~)~"
To summarise the results of Sections 3.2 and 3.3, we may recognize that the maximal
amplitude principle combined with the simple short-range interaction model (3.1.1) enables
the prediction the atomic structure of stable oxides and some fluorides with fixed stoichi-
ometry corresponding to integer valency of metal. In the case of titanium oxides, the theory
results in correct structures for all observed bcc-related oxides for Ti atom with integer
valencies, + 3 and + 4: the rutile structure, the ~-PbO2 structure, and the corundum structure.
What is more, the theory does not yield "wrong" structures which would be observed.
*It should be emphasized here that the choice of the distribution (2.4.6) rather than (2.4.5) for (3.3.44) was made
to meet the valency conditions (3.2.1), otherwise the oxide
[MI/61-15/6][Mt/6[]5/6]O=MI/30 or MO 3
corresponding to the sixvalent metal state would be expected.
tThe corundum structure based on the bcc host lattice and its patent superstructure depicted in Fig. 8(a) is
unstable with respect to the bcc--.hcp diffusionless host lattice rearrangement. As shown in Section 3.2.1, this
rearrangement does not produce Ti atom displacements from Ox and Oy interstices.
To end this section, let us note that in the Ti-O system, apart from the above "classical"
oxides with fixed stoichiometries provided by integer valencies of metal atoms, there are
oxides where metal atoms have variable valencies. As will be shown in the next section, the
maximal amplitude principle works in this case again and enables the determination of the
main structural characteristics of oxides, and explains why these oxides form the series of
homologous compounds, TinO2,_ 1-
3.4. The bcc-Lattice Based Homologous Series of Titanium and Vanadium Oxides
A large number of phases having an intermediate composition between TiO2 and Ti203 and
variable valencies of metal have been found to occur in the Ti-O and V-O systems. These
phases described by the same formula, MnO2,_, at n = 3, 4, 5. . . . . form a homologous series
which was first studied in detail by Magneli and co-workers .~,l-~4)
It has been shown in Sections 3.2 and 3.3 that the rutile structure, TiO2, and corundum
structure, Ti203, may be theoretically derived as tertiary interstitial superstructures formed
by ordering of Ti atoms over Ox and Oy octahedral interstices of the bcc host lattice composed
of oxygen atoms.
Since the rutile and corundum structures are, in fact, the extreme cases of homologous
phases at n = ~ and n = 2, respectively, it is quite natural to assume that all the homologous
phases in the Ti-O system may also be treated in terms of tertiary ordering of Ti atoms in
the bcc host lattice.
To determine the structure of homologous phases and propose the mechanism of their
formation, let us recall some facts which have been discussed in Section 2.5. Apart from the
phases with fixed stoichiometries considered above (they are generated by the dominant waves
with a wave vector multiplicity, s, = 2, 3, 4), the less stable homologous phases for which
Sl = 2n - 1 where n = 2, 3, 4, 5. . . . may also be formed. The homologous phases, unlike the
phases with fixed stoichiometries, cannot be described in terms of dominant waves alone.
Indeed, for the density function n(p, R), to assume only two values, either 0 or 1, at all
interstices {p, R} (this is the necessary condition in description of a completely ordered
superstructure), we have to introduce into n(p, R) some complementary nondominant
concentration waves. As follows from the maximal amplitude principle, a stable super-
structure in the bcc host lattice should be a layer phase consisting of alternating parallel
planes, completely filled by interstitial atoms or completely vacant. The sequence of filled and
vacant planes is also determined from the maximal amplitude principle utilizing a clock
diagram of Fig. 1.
3.4.1. Derivation of stoichiometric formula for homologous series

Consequently, we shall assume the homologous phases in the Ti-O system to be tertiary
superstructures arising in the non-stoichiometric secondary parent superstructure of Fig. 8.
This means that interstitial Ti atoms prove to be tertiary ordered over Ox and Oy interstices
"permitted" for occupancy in the secondary parent superstructure
[M,/2 [] ,/z][M,/z [] ,/2]O (3.4.1)
described by eq. (3.2.47). The formulae within the first and second pairs of brackets in (3.4.1)
show the ratios of interstitial M atoms and their vacancies, I-1, within the Ox and Oy
sublattices of the bcc host lattice, respectively. The subscripts indicate that M atoms and their
vacancies occupy one half of Ox and Oy interstices.
Let the fraction of occupied "permitted" interstices, Ox, be Cl and the fraction of occupied
"permitted" interstices, Oy, be c2. The stoichiometric formula of the corresponding tertiary
superstructure may be then obtained from (3.4.1) merely by substituting Mct l]l_cl and
Me2 [])-c2 for M into the first and second pair of brackets, respectively. The result is
[(Mc~ VII _ ~)1/2 [] 1/2][(Mc~ I-q1_ ~2)1/2[] 1/2]O. (3.4.2)
It follows from eq. (3.2.59) that the components
9(_)(1, r) = ~(_)(1, k2)e a~k: and c-p(_)(2,r) = ~(_)(2, k2)e '2~k: (3.4.3)
of the dominant wave, ?p(_)(p, r), generating the tertiary superstructure have the same
modulus and thus differ from each other only in the phase multiplier, e i~, where ~ is the phase
shift. In this situation, both components in (3.4.3) of the dominant wave ?Pc-)(P, r) generate
the same layer distribution n(1, r) and n(2, r) in "permitted" interstices of the Ox and Oy
sublattice, but these distributions are shifted as a rigid body with respect to each other by
a reference vector T, determined by the phase multiplier, e L (see for example the corundum
case considered in Section 3.3.3). In other words, we have
n(1, r) = n(2, r + T). (3.4.4)
It follows from eq. (3.4.4) that the fractions of occupied "permitted" O~ and Oy interstices
c) and c2, corresponding to the distribution n(1, r) and n(2, r) respectively are equal to each
other, i.e.
¢ ) "~- C 2 = C . (3.4.5)
Substituting (3.4.5) into (3.4.2) yields
[(Me [] ) _ ~)1/2[] 1/2][(M~ •) _ c)1/2[] 1/2]O. (3.4.6)
As is shown in Section 2.5, the value of the dominant wave amplitude (and, therefore, the
maximum stability of the phase) are at their maximal when
n n
c = c) = c: . . . . (3.4.7)
s) 2n - 1
wheren=2, 3, 4 . . . . . and sl=2n-1 (3.4.8)
is the period of the layer tertiary superstructure expressed through the number of filled and
vacant planes s) = 2n - 1 forming the translational motif. Using (3.4.7) in (3.4.6), we have
the stoichiometric formula:
[ ( M ~"i []I-.~)1/22~_,[]1/2] [ ( M ~ - t []) - ~"-~-t)1/2 ["-]1/2]0

=[M ° []3~-2][M . []3.-2]0. (3.4.9)
2(2n - 1) 2(2n - I) 2(2n - I) 2(2n - I)
Omitting the vacancy symbol, [], in (3.4.9), we obtain
M .2n-I 0 or M.02._) (3.4.10)
Therefore, the stoichiometric formula M, O2~_ 1 directly follows from the maximal amplitude
principle and explains why the homologous series of the type of TinO2,_l are formed.*
*It should be mentioned, however, that such layer structures are less stable than structures with the fixed
stoichiometry corresponding to sl - 2, 3, 4, since the former have nonzero amplitudes of nondominant waves.
3.4.2. Sequence of filled and vacant planes in homologous layer phases, Mn 02~_ 1
Once the stoichiometric formula of the homologous phases in Section 3.4.1 which was well
established experimentally is derived we should determine the sequence of filled and vacant
parallel planes forming the translational motif of the layer phases, MnO2n-~.
To illustrate the procedure, we shall analyze one of the homologs, TisO 9 for the case of
n = 5. With n = 5 eq. (3.3.29b) for the wave vector k2 of the dominant wave reads
n
k2 - 2n - 1 Hr = ~H~
5 (3.4.11)
where
Hr = 2kr + 2/-/,
kr = (½ ½0), (3.4.12)
and H is a reciprocal lattice vector of the parent secondary superstructure. In addition to the
fundamental reciprocal lattice vectors related to the bcc host lattice, vector H also includes
superlattice vectors differing from kt = (½ ~-0) by a fundamental reciprocal lattice vector, H ~ .
The layer structure of the Ti509 phase is formed by the same layer distributions in both
the Ox and Oy bcc sublattices. Both are generated by alternating parallel planes drawn in the
appropriate bcc sublattices of interstices, Ox or Oy. Some of these planes are completely filled
with Ti atoms, the remainder are completely vacant. The translation motif of the periodically
alternating planes consists of s~ = 2n - 1 = 2 x 5 - 1 = 9 planes. In determining the structure
the question has to be answered: which plane entering the motif is occupied by Ti atoms and
which is vacant?
As follows from Fig. I (b) [see also (2.5.19)], the maximum amplitude of the dominant wave
generating the layer structure with a period Sl = 9 is provided with the same sequence of filled
and vacant planes drawn in the Ox and Oy octahedral sublattices which may be symbolically
represented as the series:
F - - - - - - 7 F - - - - - - ~
Ti[]Ti[]Ti[]Ti[] I TiTi i [ ] T i O T i O T i [ ] i TiTi i . . . (3.4.13)

L _ _ _ ] L-- ---- J
I~- s1=9-- *1
where Ti denotes a completely occupied plane and [] completely vacant. The obtained Ti5 09
structure completely coincides with the result of the X-ray structure determination. °6)
The series (3.4.13) shows that filled and vacant planes in the stable homologous phase
alternate. This regular sequence has, however, faults falling at each ninth plane.* These faults
are indicated in (3.5.13) by a dashed line. Faults in the regular sequence of planes may also
be interpreted as interstitial plane defects in the rutile structure, because the defect may be
produced by inserting an extra plane filled with Ti atoms. A similar modulation pattern
follows from the maximal amplitude principle for other homologs of the series.
3.4.3. Determination of alternating plane indexes

Since the sequence of filled and vacant parallel planes is already determined, the further
refinement of the homologous phase structure requires determination of the Miller indices
of these planes. In terms of the proposed concentration wave formalism this means that we
must determine either the wave vector k 2 o r the reciprocal lattice vector Hr related to k 2 by
eq. (3.3.29b). This is the most ambiguous point in our discussion because the choice of the
*Alternation ...Ti [] Ti [] Ti... without faults would provide the rutile structure TiO2.
vector k 2 requires more detailed information about interatomic interaction, than that
contained in the short-range interaction model (3.1.1). Nevertheless, even an approximate
short-range interaction model leads to determining the most probable vectors kz and thus the
most probable planes generating the layer superstructure. By the definition of the first
Brillouin zone, any vector z in the first Brillouin zone meets the following conditions
-½1 H I ~<~,,,,~½1H I (3.4.14)
where H is any reciprocal lattice vector, nu = H / H the unit vector parallel to the vector H.
Since the vectors z are defined within the first Brillouin zone of the parent secondary
superstructure and kl = (!2 2i-0) is the shortest superlattice reciprocal vector of this super-
structure, we may rewrite eq. (3.4.14) in the form
- ½ [ k l I <<,znk,<<,½lk~ I (3.4.15)
where
.,
is the unit vector parallel to kl = (½ ~ 0).

With
+ ( _ 1): = 1
nk, = ./~,0 and I kl I =
we may rewrite the inequality (3.4.15) as follows

1 1
2.--~ <~tx - ty 2~/2" (3.4.16)
v-
Substituting formula (3.3.28) into (3.4.16) yields
1
--<< nrx--nry 1
~< 2x/~ (3.4.17)
2w/2 x//-2-2(2n - 1)
or
1H, x-H~y l
(3.4.18)
2 ~< 2(2n - 1) ~< 2"
In the case (3.4.18)
n,x-n,~>. 0
cos ~ 2(2n - 1) -/
and therefore the condition (3.3.35c) can be satisfied only if

7T
- cos 5 (n,x - t4ry) = 1
i.e. when
I H,x -- H,y I = 4l + 2 where l = 0, 1, 2 . . . . . (3.4.19)
To choose the correct H, vector from a series meeting the condition (3.5.19), the interatomic
interaction of interstitial atoms must be considered. The short-range interaction model (3.1.1)
suggests that the most stable phase has the rutile structure characterized by the wave vector
1
of the dominant wave, iHr, which, according to (3.3.25), may either be equal to k, or differ
from it by a reciprocal lattice vector of the parent superstructure. This means that the absolute
minimum of the spectrum 2(_)(k) of the matrix Wl,q(r - r') defined at "permitted" interstices,
{p, r}, of the parent secondary superstructure falls on k = ½Hr. A refinement of the
short-range interaction model, for example, by including long-range interaction caused by
conduction electrons or strain-induced interaction (6,s) may shift the absolute minimum
position of ~(_)(k) from the point ½Hr to some nearest point ½Hr+ ~. The only assumption
to be used about the long-range interaction is that this interaction makes the shift vector
magnitude much shorter than the magnitude of the vector kr = (½ ½0) i.e.
z <<kr. (3.4.20)
As follows from eq. (3.3.28), the inequality (3.4.20) is provided by the small magnitude of
the vector H~ and large number n. To choose small In l, we should assume that l = 0 in
(3.4.19). Therefore, the vectors Hr should be selected from Table 1 so that the conditions
Inrx-Hryl < 2 n - 1 at H,.x-H,.y=2
be satisfied.
These conditions may be rewritten as
Hrx - H~y = 2 and n >~ 3.* (3.4.21)
The selection of low index vectors Hr [to provide small IHr[] from Table 1 which meet the
condition (3.4.21) yields the following series
Hr= (200)b~, (lI2)b~, (312)b~o..., (3.4.22a)
where the crystal lattice plane indices, (H,.xH,yHr,) denote the bcc host lattice. For the rutile
axes, these planes have indices:
H~= (ll0)rut, (101)rut, (121)~t,... (3.4.22b)
The indices in the "bcc" and "rutile" representation are related by the equations
/-/rut = 1 He~ (3.4.23a)

0
i.e.
( H r u t ) x --~ l [ ( H b c c ) x -- (Hbcc)y], (Hrut)y = l [ ( H b c c ) x 21- (Hbcc)y], (Hrut)z = / ( H b c c ) z. (3.4.23b)
The series of planes (3.4.22) is terminated to meet the requirement (3.4.20):
__z= x/~ H,<<I (3.4.24)

kr 2(2n - 1)
which follows from
1 1
=2(2n-1)H' and kr=~.
Equation (3.3.29b) lead to wave vectors k: from the series (3.4.22a)

n n n
k2 = 2n - 1 (2 0 0)bcc, 2n----~--1 (1 i 2)b¢c, 2 n ~ (3 1 2)~. (3.4.25)
*The case n = 2 corresponding to the corundum structure was considered above.

To select the true wave vector k 2 of the dominant concentration wave from the series
(3.4.25), we must utilize the condition that this wave vector provides the ~_)(k) minimum.
An unambigious selection of the wave vector k2 cannot, however, be made (at least at the
present time), since we have insufficient information on the interatomic interaction.* In this
situation we have to adopt the plausible assumption that the true vector k2 should be sought
between the most probable vectors given by the first terms of the series (3.4.25). This
conclusion is consistent with the X-ray observations. 03)
The smallest value of n is n = 3 [see (3.4.21)]. The case of n = 3 is observed for two
structures, Ti305 and V305. Both of them are generated by the (1T6)b~ plane (i.e. (103)~ t
plane). Regardless of the fact that in this case the requirement (3.4.24) is not satisfied [we
have here small n and large IH,I], the (1T6)~ plane nevertheless meets the conditions (3.4.21)
and thus enters the series (3.4.22a). At 4 ~<n ~< 10, the (312)~ plane (i.e. the (121)~t plane)
entering (3.4.22a) generates the homologous series, Ti, O2~_~ and V, O2~_~.~1~.27)At n > 10, the
homologous series Ti, O2~_~ and V, O2~_~ are already generated by the (424)~ plane (i.e. the
(132)~t plane) which also figures in the sequence (3.4.22a). All observed homologous phases
in Ti-O and V-O systems are layer structures generated by a plane associated with the
reciprocal lattice vector H, meeting the conditions (3.4.12) and (3.4.21) and thus entering the
series of planes (3.4.22a). Unfortunately, as of yet we cannot find an unambigious relation
between the number n enumerating members of the homologous series and the plane
H~ = (H, xH, yH~z) generating the layer structure of the homologous phase. As was mentioned
above, this narrow scope of the theory is attributable to lack of information concerning
interatomic interaction.
3.4.4. Mutual positioning o f interstitial Ti atoms in the Ox and Oy sublattices

To accomplish the structure determination of the homologous phase, the mutual positions
of the interstitial atom distributions in the Ox and Oy sublattices should be found. As shown
in Section 2.2, the stable phase structure is always determined by the dominant concentration
wave,
~p~_)(p, r) = ~<_)(p, k2) exp(i2nk2r) (3.4.26)
where the "polarization vector" ~_)(p, k2) describes the contribution of the dominant wave
into the distribution of interstitial atoms in "permitted" O~ interstices when p = 1 and in Oy
interstices when p = 2.
Since
n
kz= 2n - 1 H,,
it follows from eq. (3.3.35b) that
_ cos rc(k2x - k2y) = 1.
(3.4.27)
I cos ~(k2~ - k2y) I
Substituting (3.4.27) into eq. (3.2.59) gives
1
o~_)(p, k2) = ~ (1, exp(-irc(k2, - k2y)))
x/z
or
*The problembecomesespeciallydifficultat large n when all vectorsk2in (3.4.25)tend to the same "rutile" point
½Hr.
where a~ and a2 are unit reference vectors of the bcc host lattice along the [100]b~¢ and [010]b=
directions, respectively. Substitution of eq. (3.4.28) into (3.4.26) yields
f ~ l e'2nk2r if p=l
~{_)(p, k2)ea~k: ' = ~ x/~
1 e_a=k:{,,_,2)/2ea=k:' if p = 2 (3.4.29)
Let us introduce the bcc host lattice translation

T = n(a2 - al). (3.4.30)
Then
et2~k2r = eJ2nk2n(a2-aO ~ e--12nk2(al--a2)/2 e--t2nk2(2n--1)(al--a2)/2 (3.4.31)
Since
n
kE=--H~, we have k2(2n - 1 ) = n H , (3.4.32)
2n - 1
e~2nk2r = e - i2nk2(al - a2)/2 e- a~,u, (~ - a2)/2= e- a~k2(~- a2)/2 e- iTtn(Hrx - Hry ). (3.4.33)
According to (3.4.21), Hrx - H~y = 2. Using the latter in the right-hand side of eq. (3.4.33) we
have
e- i.~**,x- n,y~= 1
and
ei2nk2 T : e - z2nk2(al - a2)/2. (3.4.34)
Substituting eq. (3.4.34) into (3.4.29) results in
I 1l~2e'~k2'
- if P =
~(_~(p, r) = ~(_~(p, k2) ea'k2" =
~_ x/~ ei2=k2(r+ r~ if p = 2. (3.4.35)
Equation (3.4.35) shows that the dominant wave (3.4.26) generates the same ordered
distribution in the Ox and Oy sublattices, the distribution in the Oy sublattice being, however,
shifted with respect to that in the Oy sublattice by the reference vector - T given by
eq. (3.4.30) (the distributions n(1, r) and n(2, r) are related to each other by eq. (3.4.4)). In
other words, if an Ox interstice, (1, r), referred to the host lattice site r is occupied by a Ti
atom, a Ti atom also occupies the Oy interstice, (2, r - T), referred to the host lattice site
r - T. This condition, combined with the known sequence of occupied and vacant planes
within the O x and Oy bcc sublattices, lead to the atomic structure of any homologous phase,
Ti~ O2n_1.
3.4.5. An example: the structure of the Ti509 phase
For illustration, let us consider again the structure of the Ti 509 phase belonging to the
Ti, O2,_~ series. It was shown in Section 3.4.2 that this phase is a layer structure formed by
alternating completely filled and completely vacant planes drawn in the bcc Ox and Oy
sublattices of the bcc host lattice composed of O atoms. These planes form the same sequence
(3.4.13) within both sublattices, the motif of the sequences in the Ox and Oy sublattices
consisting of Sl = 2n - 1 = 2.5 - 1 = 9 planes. The ordered layer distributions of Ti atoms
in the Ox and Oy sublattices, n(1, r) and n(2, r), are related to each other by eq. (3.4.4) where
the shift reference vector, T, is given by eq. (3.4.30). The layer structure, Ti509, is originated
by the alternating plane, (312)b~c= (121)r~t.
According to Section 2.3, the reciprocal lattice of this structure should be described by
superlattice diffraction spots which divide all Hr = (312)~ reciprocal lattice vectors into s~ = 9
equally large segments. Fig. 12(a) display the reciprocal lattice pattern and Fig. 12(b) the
atomic lattice of the Ti5 09 homolog which follow from the above reasoning. One may easily
see from Fig. 12(b) the orientational relations between the bcc host lattice frame composed
of oxygen atoms and the lattice of the Ti5 09 superstructure. The size of the reciprocal lattice
points in Fig. 12(a) is chosen to be proportional to the diffraction intensities calculated for
the derived superstructure in Fig. 12(b) (atomic displacements are not taken into account).
The size of the superlattice points, by definition, is proportional to the value tap(S)[ 2 of
(2.5.17).
Table 2 enables comparison the relative intensities of the diffraction lines obtained on the
powder diffraction pattern (~2)and intensities in arbitrary units which follow from eq. (2.5.17).
One may see that Table 2 demonstrates the good agreement between X-ray data and
calculated results, even though the displacements of oxygen atoms are disregarded. The same
agreement is observed between the proposed model and the single crystal X-ray data. It
should be emphasized that X-ray data confirm that the intensities of the superlattice
reflections generated by the dominant concentration waves (Hsu~rl = k2 + H ) assume the
maximum values.
3.4.6. Summary
Summing up the foregoing discussion, the theoretical analysis in terms of the maximal
amplitude principle results in correct prediction of the structure of homologous phases, in
particular:
(i) the layer structure in the Ox and Oy sublattices with the correct sequence of filled
and vacant parallel planes of the type of (3.4.13);
(ii) the correct mutual positioning of these sequences in the O~ and Oy sublattices
determined by the shift vector (3.4.30);
(iii) short list of the most probable planes Hr whose alternation originates the layer
structure, the planes (312)~, (1T6)~c and (424)~c observed for the homologous
series Ti, Oz,_l and V,O~_~ entering this list.
Concluding this section, let us have a closer look at an interesting fact concerning the
homologous series. The proposed interpretation of the homologous phases is readily seen to
differ from the conventional one in which the crystallographic shear mechanism is assumed. (~3)
According to the latter, a homologous phase is obtained from the rutile structure by the
crystallographic shear along the parallel regularly spaced shear plane. It is of interest to note
that the Miller indices of the shear plane completely coincide with the indices (HrxHryHrz)
of the plane H, describing the above alternation of filled and vacant planes.
Although the atomic structures of the phases, Ti, O2,_~ and V, O2,_~, following from both
interpretations are the same, the proposed energy approach proceeding from the fact that the
homologous phases are long-period interstitial layer superstructures in the bcc host oxygen
(a)
3f2
000 '~ _ l ~,~0

¢~0
(b)
0 o~
\\
\ 0
\
~7 ao~, e s,s. 78 o\,',~a '~5 6 7 ~1 0 pE~ne(3ft)tz~ce
[oO~)t=plane
FIG. 12. (a) Diffraction pattern of the bcc-based interstitial superstructure corresponding to the
homologous phase, Ti~Og. The ( I l l ) plane of the reciprocal lattice. Superlattice diffraction spots
divide the directions [312] into equal segments, the spot size being proportional to the diffraction spot
intensity. Spots at points ~4 (312) and ~5 (312) corresponding to the conjugate superlattice vectors k 2 and
-k2 of the dominant waves have largest intensities. (b) Crystal lattice in the (001)~ plane of the
bcc-based interstitial superstructure corresponding to the TisO9 homolog. ©, Oxygen atoms forming
the bcc host lattice; @, metal atoms in Ox, O, metal atoms in Oy octahedral sites. Solid lines show
the traces of the (312)b~ planes filled by Ti atoms, dash lines show the traces of the vacant (312)~
planes. Heavy lines indicate components of antiphase domains in the rutile structure.
lattice seems to be m o r e realistic. I n p o i n t o f fact, m u t u a l t r a n s f o r m a t i o n s b e t w e e n rutile,

ct-PbO2 structure, c o r u n d u m a n d h o m o l o g o u s p h a s e s are r e d u c e d in this a p p r o a c h to m e r e
r e d i s t r i b u t i o n o f Ti interstitial a t o m s within o c t a h e d r a l interstices o f the s a m e h o m o g e n e o u s l y
d i s t o r t e d bcc h o s t lattice f r a m e c o m p o s e d o f o x y g e n a t o m s . It d o e s n o t require artificial
i n t r o d u c t i o n o f a c r y s t a l l o g r a p h i c s h e a r involving the c o o p e r a t i v e m o v e m e n t o f Ti a n d O
T a b l e 2. Comparison of the Relative Intensities of X-ray Diffraction Lines of Ti509 with Calculation
Results
Harmonics,
Conventional ReflectionIndices s, of the Relative Intensity
Indices Related to the bcc wave vector
N O dt A ° (HxHyHz)homolog Host Lattice k2=~(312) Observations cm Calculations
1 7,81 001 ~112 2 vw 2,8

2 5,19 10I _r!_~
263 3 w 10
3 4,71 100 T5
6 1 8 95 4 vw 4,2
4 4, 03 10~ ~6 1 8191 1 st 83
5 3,42 101 177
6189 2 vw 2,8
6 3, 36 120 T7T
6189
1 vst 83
7 3,34 02I _r
3 9_r
9 _~ 4 vw 4,2
8 3,23 020 0~{ 3 w 10
9 3,12 I21 ~t31 3 w 10
10 3, 07 121 119 I
6189 1 vst 83
11 2,94 022 _~_T_2
399 2 w 10
12 2,91 10~ "rI'T
6189 1 vst 83
13 2,72 021 ~1~8 1 m 83
14 2,60 20I ~4~ 1 st 83
15 2,58 122 ~95 4 vw 4.2
(nxnynz)homolog = ~ lJ|n, /
½1\n,l~
vw, very weak; w, weak; m, medium; st, strong; vst, very strong.
atoms which would be difficult to explain. The mechanism of formation of a homologous

phase in the proposed model is the same as the conventional mechanism of an interstitial
ordered phase formation. It is nucleation-and-growth provided by the redistribution of
interstitial atoms within the host lattice framework. Such a conventional mechanism seems
to be more attractive and plausible than the complex mechanism of shear plane formation
involving planar aggregation of host lattice vacancies.
Finally, what is most important, the proposed theory has the predicting ability. It enables
the determination of atomic structures of the phases occurring in the Ti--O and V-O systems
on the sole assumption that all these phases are interstitial superstructures, meeting such a
simple kinematic concept as the maximal amplitude principle.
We shall demonstrate below that this approach proves to be very fruitful in the case of
the fcc-based phases as well as in the case of the bcc-based phases.
4. STABLE CERAMIC COMPOUNDS BASED ON THE FCC

HOST LATTICE
Besides t h e b c c - b a s e d c e r a m i c o x i d e s d i s c u s s e d in C h a p t e r 3, t h e r e is a n o t h e r g r o u p o f
o x i d e s b a s e d o n t h e fcc h o s t lattice. T o w i t h i n s m a l l a t o m i c d i s p l a c e m e n t s a n d h o m o g e n e o u s
strain, a t o m s in t h e s e o x i d e s o c c u p y c r y s t a l lattice sites a n d i n t e r s t i c e s o f t h e fcc lattice. It
s h o u l d b e n o t e d t h a t t h e s i t u a t i o n w i t h all fcc h o s t lattice sites v a c a n t w h e n a t o m s c a n o c c u p y
o n l y i n t e r s t i c e s is a l s o p o s s i b l e . A t o m s in t h e f c c - b a s e d s t r u c t u r e s c a n n o t , as a rule, t r a n s f e r
b e t w e e n i n t e r s t i c e s o f d i f f e r e n t t y p e s o r b e t w e e n i n t e r s t i c e s a n d c r y s t a l lattice sites.
There are two types of crystallographically nonequivalent interstices whose volume is

sufficient to be filled with interstitial atoms, octahedral and tetrahedral interstices (Fig. 13).
There is one octahedral interstice per fcc lattice site which is displaced with respect to the
fcc lattice site by a distance
h 0 = l ( a I -q- a 2 q- a 3 )
where al, a2 and a 3 are the unit translation along the [100]fo~, [010)f¢¢ and [001]fo~ directions.
Therefore, copying this interstice by means of fcc Bravais lattice translations results also in
the fcc sublattice of octahedral interstices which is shifted with respect to the fcc-host lattice
by a distance h0 [Fig. 13(a)]. When all fcc lattice sites are filled with atoms of the first type,
and all octahedral interstices are filled with atoms of the second type, the NaC1 structure
occurs (see Fig. 6). More complex binary compounds may be obtained when the formation
of structural vacancies and their ordering is involved. The problems associated with the
theoretical determination of these structures will be considered below.
As for the second type of interstices in the fcc host lattice, tetrahedral interstices, there are
two tetrahedral interstices per fcc lattice site which are symmetrically related. They are
displaced from the fcc host lattice site by the distances:
hTl ---- 41-(al "b a2 + a3)
hT2 = -- l(al + a2 + a3).
Each of these two tetrahedral interstices multiplied by fcc Bravais lattice translations
produces its own fcc sublattice. We shall refer to interstices of the first such sublattice as
tetrahedral interstices of type TI and to interstices of the second sublattice as tetrahedral
interstices of type T2. The first tetrahedral fcc sublattice, T1, is shifted with respect to the fcc
host lattice by the distance hTi. As for the second tetrahedral fcc sublattice, T2, it is shifted
by the distance hrs. Both sublattices, TI and T2, may be brought into coincidence by symmetry
operations of the fcc lattice, and thus are crystallographically equivalent [see Fig. 13(b)]. If
all fcc lattice sites are occupied by atoms of the first type, for example, by A atoms, and all
tetrahedral interstices of type T1 and T2 are occupied by B atoms, a fluoride structure with
a stoichiometric formula AB2 arises. In the prototype fluoride structure CaF2, Ca atoms
occupy fcc lattice sites whereas F atoms occupy all tetrahedral interstices (Fig. 14). In the
case of oxides, the fluoride structure occurs for ThO2, CeO2, ZrO2 and other quadrivalent
metal oxides. (19)When metal valency does not fit the stoichiometric formula MO2, the valent
relations between M and O atoms are maintained by removal of metal or oxygen atoms from
(a) (b)
_ _
I
I I
t
I
I
~ _~--~-~ _
i I I
I
~ , ~ _
,it
FIG. 13. (a) Octahedral and (b) tetrahedral sites in the fcc host lattice.
FIG. 14. The CaF2-type superstructure. The fcc host lattice is composed of Ca atom, two tetrahedral
sublattices, T I and T2, are completelyfilled with F atoms. O, F; ©, Ca.
the MOz fluoride structure. The ordering of structural vacancies thus formed may generate
much more complex structure than the parent fluoride structure.
Below we shall consider the most widespread type of oxides in which the valency of metal
atoms is less than + 4. Structural vacancies in this case will arise in the oxygen sublattice,
i.e. in T1 and T2 tetrahedral interstices. The most general formula for such a type of oxide
is
M[Ol-c,[]c,][O1-c2[]c2] or MO2-c,_~2.
The symbols O1 _c, []~2 within the first pair of brackets describe the relation between O atoms
and their vacancies [] in the T1 sublattice, the symbols within the second pair of brackets
describe the same relation in the T2 sublattice.
If the host lattice sites are filled with two species of metal atoms, M' and M", forming a
substitutional binary solution within the fcc host lattice, the oxide formula becomes
(M', M")[O1_¢, ~¢,] [O,_¢2~ j .
Finally, still another type of the fcc-based structure may also be formed. This is the "mixed"
structure in which both tetrahedral and octahedral interstices are filled. The spinel structure
is a good example of such "mixed" structures.
4.1. Interaction of Interstitial Atoms in Tetrahedral Interstices of the fcc Lattice

4.1.1. The characteristic matrix in the case of tetrahedral interstice occupancy
It follows from Fig. 13(b) that each tetrahedral interstice Tt in the fcc lattice is surrounded
by six nearest tetrahedral interstices of type T 2 separated from the original T~ interstice by
a distance rl = la. The second coordination shell with radius
a
r 2 - - N/~
has 12 T1 interstices, and the third coordination shell with radius
,fi
r3 = ---~- a
has 8 T2 interstices where a is the fcc lattice parameter.

Since the sublattices TI and T2 are crystallographicaUy equivalent, the characteristic matrix
J.P.M.S.29/I-2--F
Vpq(k) defined in eq. (2.1.5) is
Veq(k) = ~ Wpq(R) exp(-i2r~kR) = ( vll (k) V12(k)~ (4.1.1)

\Vl2(k)* Vii ( k ) ]
where the numbers 1 and 2 assumed by indexes p and q are referred to tetrahedral interstices
of types T~ and "1"2, respectively; Wpq(R- R') is the interaction energy of two interstitial
atoms at interstices (p, R) and (q, R'). As was mentioned above during the analysis of the
bcc-based structures, we do not have enough information about interatomic interaction in
chemical compounds. That is why the simplest model of the nearest, next-nearest and
next-next-nearest neighbor interaction will be accepted. Because interstitial atoms in ceramic
compounds are ions, one may assume that interaction of two atoms separated by a short
distance is repulsive. This interaction is a combination of "contact" interaction caused by
"overlap" of electron shells of ions (exchange interaction) and electrostatic Coulomb
interaction screened due to polarization of electron shells of atoms and atomic displacements.
In the three coordination shell model, interaction energies for interstitial atom pairs vanish
when the interatomic separation distance exceeds the third coordination shell radius,
r3 =a 2
The nonzero interaction energies associated with the shorter separation distances
1 a x//3
rl=~a, r2=-~ and r3=a 2
are assumed to be equal to W1, W2 and W3, respectively. These values are positive because
of repulsive interaction of interstitial atoms. The natural assumption on decreasing inter-
action of interstitial atom pairs when separation distance increases may, thus, be reduced to
the inequalities
I4"1> W2> W 3 > 0 (4.1.2)
and IV,.= 0 when i > 3.
Substituting the nonzero interaction energies into eq. (4.1.1), we have
Vii(k) = ~ WII (R) e x p ( - i2rckR) = 4W2[cos rtkx cos rtky

R
+ cos rckxcos nk z + cos r~kycos rck~](k) = V22(k) (4.1.3a)
Vlz(k) = ~ W12(R) exp ( - i 2rtkR ) = [2 Wl (cos rck:,+ cos rcky+ cos rck~)
R
+ 8 W3 cos zckx cos rckycos nkz] exp(in(kx + ky + kz)) (4.1.3b)
where
1
k = - (ak x , Icy, k~).
4.1.2. Eigenvalues and eigenvectors of the characteristic matrix

Since the structure of matrix (4.1.1) is identical with that of the matrix (3.2.57), its analysis
is similar to that performed in Sections 3.2 and 3.3. Both matrices, (4.1.1) and (3.2.57), have
two branches of the eigenvalue spectrum:
) = Vll(k ) +_ l Vl2(k ) l , (4.1.4)
We are interested in the lower branch of the spectrum,

2f_)(k) = Vn(k)- I V12(k) I (4.1.5)
because the desired dominant wave corresponds to the minimum eigenvalue.
The eigenvalue (4.1.5) is provided by the eigenvector
o<_)(p,k)=(o(_)(1,k), o(_)(2, k))=~--~

1 ( 1, I (4.1.6)
[cf. eq. (3.2.59)].

Substituting eq. (4.1.3) into eqs (4.1.5) and (4.1.6) yields:
2(_)(k) = 4W2 [cos nk,, c o s Itky+ COSnk,, cos r~kz + c o s xky cos rrkz]
- [ 2 W1 [cos rtkx + cos rrky + cos nk~] + 8 IV3 cos nkx cos ltky cos nk~ I (4.1.7)
and
1 (1, - 2Wt[cosnkx+cosrrky+cosnk~]+8W3cosnkxcosnkycosrrk~
o(_)(p, k)
12Wl [cos nkx + cos rtky + cos nk~] + 8W3 cos nkx cos nky cosnk, I
X e -in(kx+ky+kz)) (4.1.8)
According to eq. (2.3.3), the wave vector k0 of a dominant wave may always be represented
as
ko = H/sl (4.1.9)
where st is the least integer which, when multiplied by the vector k0, yields a reciprocal vector
H of the fcc host lattice. As was shown in Section 3.3., the condition of the maximum of the
dominant wave amplitude imposes certain constraints on the vector /Co. In particular, it
should meet the equality (3.3.6) which in the case under consideration reads
( Vl2(ko)*) st
[ V,2(ko) l = 1 (4.1.10)
Substituting eq. (4.1.3) into (4.1.10) gives

_ 2W~ [cos nk0x + cos nkoy + cos nko,] + 8 W3 cos nkox cos nkoy cos nko~
I I 2 Wl[cos rckox+ cos rrk0y + cos nko,] + 8 W 3 c o s nk0~ cos nkoy cos nk0~ I
],l
xe-~(k°~+~Y +k°') = 1 (4.1.11)
In light of the relation

H = $1 ko
following from (4.1.9), we may rewrite eq. (4.1.11) as

{ - sign[2 I4"1(cos nkox + cos knoy + cos k0z) + 8 I4"3cos rrk0x cos rrkoycos nkoz]}s,
x e x p ( - ix(Hx + ny + H,)) = 1 (4.1.12)
where the function, sign b, is defined by the relations
1 when b > 0
signb= -1 when b<0.
4.1.3. lntracrystalline field along fcc host lattice sites

As shown in Section 2.6, the ordering of interstitial atoms may generate a heterogeneous
intracrystalline field on host lattice sites. The heterogeneous field generated by interstitial
atoms in a binary fcc-based compound may break the equality of chemical potentials of host
atoms along the fcc lattice sites. In this case the system cannot be stable and various relaxation
processes such as host lattice displacements and changes in electron and spin states of host
atoms leading to equalizing the chemical potentials should be "switched on".
The situation becomes more complicated when it is the interaction between interstitial and
host atoms that is chiefly responsible for the chemical bonding of the crystal, as is the case
in crystals with ionic bonding where interstitial atoms and host atoms are oppositely charged
ions whose attraction provides atomic cohesion in the crystal. The modulation of the
intracrystalline field along host lattice sites may then become comparable with the sub-
limation energy of host atoms. Equalizing the chemical potentials along the fcc host lattice
can then occur either by generating structural vacancies in "antinodes" of the intracrystalline
field if the number and spatial distribution of vacancies do not produce the host lattice
instability or through "collapse" of the host lattice and its radical rearrangement if vacancies
result in excessive loosening of the host lattice.
In binary ionic crystals, the "loose" structures with many structural vacancies are, as a rule,
unstable. The nondirectional character of bonding results in the fulfilment of the close
packing principle and thus in radical crystal lattice rearrangement of the "loose" structure.
This is the reason that the uniformity of the intracrystalline field along the host lattice is the
necessary condition for stability of a binary crystal with ionic bonding.
The criterion does not apply to multicomponent crystals with ionic bonding when host
lattice sites are occupied by atoms of various type. In this case the necessary condition of
equilibrium should be slightly reformulated. Indeed, the equilibrium condition requires that
the chemical potentials of all atoms of the same type be equal to each other. This condition
can however be met when the intracrystalline field changes along the host lattice but assumes
the same values on sites occupied by identical atoms. Therefore, the equilibrium will be
maintained even if the intracrystalline field assumes as many various values on the host lattice
sites as there are various atoms occupying the host lattice.
In other words, the intracrystalline field assuming several different values on host lattice
sites (whose number is equal to that of types of atoms occupying the host lattice) divides all
host lattice sites into several sublattices so that the field assumes the same values within each
sublattice. Equilibrium is maintained if all host lattice sites of each sublattice are occupied
by identical atoms whereas the various sublattices are occupied by various types of atoms.
For example, when the intracrystalline field is heterogeneous and assumes two different
values on host lattice sites, the host lattice of a stable crystal must be occupied by two types
of atoms. When the intracrystalline field assumes three different values on host lattice sites,
the host lattice must be filled with three types of atoms, etc. It should be emphasized that
the modulation of the intracrystalline field along the host lattice (in these cases it divides the
host lattice sites into two, three etc. sublattices, every sublattice being completely filled with
its own type of atoms) unambiguously determines the atomic fractions of constituents and
spatial distribution of host atoms.
Let us consider the intracrystalline field generated on fcc host lattice sites by an ordered
distribution of interstitial atoms in tetrahedral interstices. Equation (2.6.3) may then be
reformulated as
7j (R) = 7to + ~ ' ~(_)(kj)V(kj) exp(i2nkjR) (4.1.13)

J
t
where 7t(R) is the value taken by the intracrystalline field on the fee lattice site at R, ~0 is
a constant,
2
V(kj) = ~ ff'p(kj)o(_)(p, kj) = ff'l (kj)o(_)(1, kj) + I~2(kj)o(_)(2, kj) (4.1.14)
p=l
is the formfactor of the field.
ff'p(k ) = ~ Wp(R) e x p ( - i2nkR). (4.1.15)

R
Wp(R) is the interaction energy between a host atom at the site R = 0 and an interstitial atom
in the tetrahedral interstice at (p, R). The summation in eq. (4.1.15) is carried out over all
fcc lattice sites. The subscripts p = 1 and p = 2 in eqs (4.1.14) and (4.1.15) refer to tetrahedral
interstices of T~ and T 2 types, respectively.
In eq. (4.1.14) the ordered distribution is assumed to be generated by the only "polar-
ization" designated by the symbol ( - ) . As was shown above, this assumption enables us to
satisfy the maximal amplitude principle. Because we shall be interested in the spatial
symmetry of the intracrystalline field, ~/'(R), rather than its concrete values, we may assume
the nearest-neighbor interaction model without the loss of generality. According to this
model, the contribution into the field ~ (R) is provided only by those interstitial atoms which
occupy the tetrahedral sites nearest the host lattice site R.
Let the interaction energy between a host atom and an interstitial atom separated by the
shortest distances ¼(_+al __ a2 +_ a3) be I410. Then eq. (4.1.15) reads
I'V~(k ) = W o e- (i,/2)(kx+ky +kz) [e(tn/2Xkx + ky + kz ) "4- e - (in/2)(kx + ky - k;: ) . ~ e - (in/2)(kx - ky + k z )
+ e- (i,/2)(-k~ + ky + kz )] = 4 Wo e- (17t/2Xkx + ky + k z )
[ Tz ~z ~ rc . rc . r~ ]
x cos-~kxcos-~kycos-~k~- i sin-~kx sin -~ k, s i n -~ k~
I~2(k) = ff'l(k)*. (4.1.16)

~'(k) = 4Wo{e -(~"/2)(kx+k, +k~)/COS kx cos.r 2~ 2~ky cos 2~k~ - i sin 2~kx sin. -2~zky sin -27zk~v(_)(l,
] k)
+k ) 7Z 7Z ~ 7~ 7~ 7~ ]
+ e(i,/Z)(kx+k~ z [COS~ k~ cos ~ ky cos ~ k~ + i sin ~ kx sin -~k e sin ~ ky] o(_)(2, k). (4.1.17)
4.2. Primary Interstitial Superstructures with Fixed Stoichiometry in Tetrahedral

Interstices of the fcc Host Lattice
As was shown in Section 2.4, the largest amplitude of a dominant concentration wave can
be attained in the cases of s~ = 2, 3 and 4 where the maximal amplitude principle is most
completely fulfilled. In these cases, when the density function n(p, R), may be constructed
so that it includes only two dominant waves, (a, ko), and ( a 0 , - k 0 ) , the corresponding
superstructures have fixed stoichiometry determined by eqs (2.4.4), (2.4.5) and (2.4.9).
The wave vector k0 of the dominant waves are determined by eq. (4.1.9). Substituting into
eq. (4.1.9) all reciprocal lattice vectors, H, of the fce host lattice at s~ = 2, 3 and 4 and reducing
the resultant vectors H/s~, into the first Brillouin zone, we obtain the following finite series
of stars which may generate the stable superstructures with the fixed stoichiometry:
{k O} ~-- (0 0 0), { 1 0 0}, {111}, { I l l o}, 311 {1½o), 1
{200}, {~iO}, {1~½}. (4.2.1)

In the particular case of the fcc host lattice, the list of suitable stars (4.2.1) should be
supplemented with two stars. It was shown in Section 2.4 that the dominant waves belonging
to the stars,
{ko} = {4 o} (4.2.2a)
(4.2.2b)
may generate the stable superstructures in the fcc lattice without complimentary non-
dominant waves.
Substituting eq. (4.2.1) into (4.1.7) at all k = k0 listed in (4.2.1) and (4.2.2) and comparing
the resultant eigenvalues 2(_)(k0) show that the minimum eigenvalue may be realized only for
two stars, {ko} = (000) and {k0} = {100}.
The function 2(_)(ko) defined by eq. (4.1.7) assumes the following values at these two stars:
2(_)(ko) = - 6 W 1 + 1 2 W z - 8W 3 at ko = (000) (4.2.3a)
and
2(_)(k0) = - 4 W z - 12W1 - 8W3[ at k0 = {100}, (4.2.3b)
The diagram of Fig. 15 indicates, in the space of variables W2/ WI and W3/ W~, the fields
where the eigenvalues related to k0 = (000) and k0 = {100} assume the minimum value. In this
diagram the inequalities (4.1.2) are assumed. The fields related to the remaining stars not
plotted, for the corresponding eigenvalues assume higher values. The latter statement is valid
at all points of the plane
~oo~ (too)zr~-RO
0
/ / , ~75 f .~
FIG. 15. Stability field diagram for the three-neighbor interaction model indicating the mutual
location of the minimum eigenvalue areas where the eigenvalues related to the k o = (000) and
k0 = {100}. The rest of eigenvalues take on lower values.
in Fig. 15 besides the point (½, ¼). In the singular point,

w2__, w3_,
W1 ~ and ~-~,
the eigenvalues ).(_~(k0) at k0 = (½ ½0), k 0 = {1 ~ -~}, k0 = (000) and k0 = {100} prove to be
equal.
It follows from the diagram of Fig. 15 that the lowest eigenvalue falls on the vector
k0 = (000) when
W~ >> W2 > W3 > O
i.e. when the repulsion of the nearest-neighbor interstitial atoms dominates over all other
interactions. The latter occurs for "large" interstitial atoms whose "contact" repulsion caused
by their overlap is most significant.
4.2.1. Atomic structure of the minimum eigenvalue related to k 0 = (000)

It follows from eq. (4.1.6) that at k0 -- (000) the dominant wave is
o(_)(p, 0) = ~/2 (1, - 1). (4.2.4)

" v
In this case, eq. (2.3.1) for the distribution function generated only by the dominant wave
reads
no(p, R ) = l c + y~_~(0)o(_)(p, 0) (4.2.5)
in the case of tetrahedral occupancy. The number of sublattices, v, is made equal to 2. The
function (4.2.5) is either unity or zero if
1
c = 1 and =
Equation (4.2.5) may then be rewritten as

R) z 1 f~ when p = 1 (T1 interstices)
no(p, (4.2.6)
=~+~o(_)(p, 0)= _ when p = 2 (T2interstices).
Placing interstitial atoms in interstices where no (p, R) = 1, we obtain a stable atomic structure
whose unit cell is depicted in Fig. 16. In this structure all T1 interstices are filled with
interstitial atoms whereas all T2 interstices are vacant. This is the so-called sphalerite structure
ZnS where Zn atoms form the fcc host lattice and S atoms occupy all TI (or T2) interstices.
FIG. 16. The sphalerite-type superstructure, ZnS. Zn atoms form the fcc host lattice, S atoms occupy
one o f the tetrahedral sublattices. O , S; O , Zn.
As mentioned above, the sphalerite structure may arise for those compounds in which the
atomic radius of interstitial atoms is so large that overlap of two nearest atoms would result
in the "contact" repulsion dominating all other interactions (W~ >> WE > W3). The increase of
interstitial atom size either stabilizes the fcc-based sphalerite structure or destabilizes the fcc
host lattice. The latter seems to be the reason why the sphalerite structure is observed only
for ZnS and ZnO under high pressure. ~37)
Incidentally, the sphalerite structure is a parent structure for the entire family of polytypic
tetrahedral structures, os)
4.2.2. Atomic structures of the minimum eigenvalue related to the {100} star
Let us have a closer look at the case when the relation between interaction energies, W~,
I4"2 and W3 are such that the minimum eigenvalue falls on k0 = {100}. In this case the
eigenvector of the matrix Vpq(k) is determined by eq. (4.1.8) at k =k0 = {100}:
1
v(_) (p, k0)k0= ~100~= ~ (1, sign (2 W 1 - 8 Wa))
Vz
f~22 (1,1) w3 1
if -~-~<~
= 1 (4.2.7)
[~22(1,-1) if W ~ > ~ •
(a) The case of W3/W1 < ¼:

In the field of the diagram of Fig. 15 where the minimum eigenvalue falls on the
k = k0 = {100}, the dominant waves have wave vectors belonging to the star {100}.
It follows from eq. (4.2.7) at W3/WI < ¼that the dominant waves related to the star { 100}
have the form:
o(_)(p, k~) exp(i2rck'oR) = ~ (1, 1) exp(i2zx)

v
1
o(_)(p, k'o') exp(i2r~kdR) = ~ (1, 1) exp(i2rcy)
I
o(_)(p, k'o") exp(i2r~k~"R) = ~ (1, 1) exp(i2r~z) (4.2.8)
where k(~=(100), k~'=(010), k~"=(001) and thus k ~ R = x , k d R = y , k~o"R=z at

R = xal + ya2 + za3: (x, y, z) are dimensionless coordinates of the fcc lattice sites. Utilizing
in eq. (2.3.1) the dominant concentration waves (4.2.8), we may construct only two functions
n (p, R) which are either unity or zero on all fcc lattice tetrahedral interstices {p, R}:
1 1 k~") e '2,~k~"'~= f l + ~1et2rtz if p = 1 (4.2.9)
n , ( p , R ) = ~ + - -x//2
v(_)(p, +~
1 _i2,z if
P
=2
and
1
n2(p, R ) = ¼+ 2 ~ 2 [o(_)(p, k•) e '2'~kaR+ v(_)(p, k;') e a'~k~R+ v(_)(p, ko") e a'~ka'R]
N'
{~ [ea"X+et2"Y+et2"q if p = l
l ++¼¼ [e a"x + e e"~' + e ':"z] (4.2.10)
= if p=2
./1 i/'r
12,¢"
w v w w
FIG. 17. The CuO-type superstructure (CuO, PrO, FIG. 18. The Cu20-type superstructure (Cu20,
PdO) generated by the O atom distribution (4.2.9) in Ag20) generated by the O atom distribution (4.2.10)
T~ and T2 tetrahedral interstices of the fcc host in T~ and T 2 tetrahedral interstices of the fcc host
lattice composed of Cu-atoms. Q, Cu; C), O. lattice composed of Cu-atoms. Q, Cu; O, O.
Placing interstitial atoms into interstices of type T 1(p = 1) and T2( p = 2) where the functions
nl (p, R ) and n2 (p, R) are equal to unity, we obtain two structures shown in Figs 17 and 18,
respectively.
Oxides described by eq. (4.2.9) have the stoichiometric formula
M[O1/2 [] 1/2] [O1/2 [] 1/2] = MO (4.2.11)
if metal atoms, M, occupy fcc host lattice sites, and O atoms occupy tetrahedral interstices.
The number i within the first and second pair of brackets shows the fraction of occupied T1
and T2 interstices, respectively. This structure, depicted in Fig. 17, is observed for the stable
polymorphs, CuO, PtO and PdO, where O atoms are interstitials.
As for the structure shown in Fig. 18, the fractions of tetrahedral interstices, T1 and T2,
occupied by O atoms are determined by the first terms of eq. (4.2.10) related to the cases of
p = 1 and p = 2, respectively. It is equal to 1/4. Consequently, we may write the stoichiometric
formula of the oxide as
M[Ol/4 [] ~/4] [0)/4 []3/4] = MO1/2 or M20 (4.2.12)
This structure drawn in Fig. 18 has been observed in Cu20 and Ag20. 09)
Note that eq. (4.2.10) may also describe the compound which is antiisomorphic to the
structure presented in Fig. 18. To obtain the atomic positions in the antiisomorphic structure,
we should substitute interstitial atoms in the origin structure for their vacancies and vice
versa, i.e. we should place interstitial atoms into interstices {p, R} where n(p, R ) = 0 and
leave interstices where n2 (p, R) = 1 vacant. The antiisomorphic structure obtained in this way
is depicted in Fig. 19. Its stoichiometric formula may be derived from (4.2.12) by substituting
the symbol O for the symbol [] and [] for O:
M [ [ ] 1/403/4] [[] 1/403/4] = MO3/2 or M203. (4.2.13)
This compound is the most stable oxide of a trivalent metal based on the fluoride lattice. The
structure M203 is observed in As203 (arsenolite), Sb203 (senarmontite), 6 - Bi203.
(b) The case of 1413/I/F1 > ¼:
In the field of Fig. 15 where the minimum eigenvalue falls on k = k0 = {100}, we have a
FIG. 19. The As203-type superstructure (As203, Sb203, Bi203) antiisomorphic to one depicted in
Fig. 18. O, O; O, M.
different situation when W3/W1 > ~. In this case, eq. (4.2.7) results in the eigenvector
o~_)(p, k0) = ~ (1, - 1) (4.2.14)
at k0 = {100}. The dominant waves corresponding to the star {100} thus have the following
form
v~_)(p, k~) exp(i2nk~R) = ~ (l, - 1) exp(i2nx)

,/2
o(_)(p, k'o')exp(i2nk'o'R ) = l (I, - 1) exp(i2ny) (4.2.15)
,/2
v(_)(p, k'o")exp(i2zk~"R) = ~ (1, - 1) exp(i2nz)
[cf. eq. (4.2.8)].

The dominant waves (4.2.15) utilized in eq. (2.3.1) help construct the only distribution
function which is either unity or zero on all fcc lattice tetrahedral interstices. This function
is
1 1
n3(p,R) ~ + ~ v ( _ ) t p ,r k
ojexp(t2rckoR)=~+~(1,-1)exp(i2gz)
tit ~t • tit 1 ]
f½+½exp(i2nz) if p = l
(4.2.16)
=),½-½exp(i2rtz) if p 2
Inserting interstitial atoms into Tt and "['2 interstices where n3(p, R ) = 1, we obtain the
structure of Fig. 20. This structure is really observed in oxides PbO and SnO where O atoms
act as interstitials. 09)
All ordered distributions of interstitial atoms generated by the star {100} produce a
homogeneous intracrystalline field on fcc host lattice sites. One may readily see it substituting
k0 = { 100} into the formfactors of the intracrystalline field (4. I. 16) which enters eq. (4.1.13)
for the field ~ (R). The conclusion is of importance because it proves the stability of the host
metal fcc lattice in face of formation in this lattice of structural vacancies, i.e. it proves that
structural vacancies should not occur in the fcc host lattice.
f7
v w
FIG. 20. The MO superstructure (PbO, SnO) generated by the O atom distribution (4.2.16) in Tt and
T 2 tetrahedral interstices of the fcc host lattice composed of M atoms. O, M; O, O.
4.2.3. Structures obtained by refinement of the model

The "roughness" of the interatomic interaction model was frequently emphasized in our
discussion of stable structures with a fixed stoichiometry. This is attributable to our lack of
knowledge of the nature of chemical bonding. For this reason one should try to see whether
the above conclusions remain true if the model is extended incorporating longer distance
interactions.
In the relevant model of the three coordination shell interaction, we have already elucidated
all consequences of arbitrary variations of interaction energies, W~, WE and I413, on the
structure formation. However, the list of structures obtained above cannot be regarded as
complete. The point is that the interaction range was assumed to be confined to a three
coordination shell radius. In a more realistic model we should incorporate larger-distant
interaction and investigate its effect on the list of structures with fixed stoichiometry.
Since the real interatomic interaction energies are unknown, the simpliest way to refine the
model is to introduce one more interaction energy, I414.The energy 14/4describes the repulsion
of two interstitial atoms in tetrahedral interstices separated by the fourth coordination shell
radius, r4 = a.
Introducing the additional energy, W4, in eq. (4.1.3) yields an additional term for the matrix
element Vu(k). Equation (4.1.3a) then reads
Vll (k) = 4 WE(COSnkx cos nky + cos nkx cos rckz+ cos lzkycos nkz)
+ 2 W4(cos 2r~kx+ cos 2nky + cos 2nk~). (4.2.17)
As for the matrix element, V~2(k), it stays invariable and, is, as above, determined by eq.
(4.1.3b). This occurs since the energy W4 is related to the interaction between two interstitials
separated by the complete fcc lattice translation, a; therefore, these interstitials find
themselves in interstices of the same type. Conversely, the matrix element V~2(k) is, by
definition, determined by interaction between interstitials occupying interstices of different
types.
Since the eigenvector in eq. (4.1.6), o~_~(p,k), depends only on Vl2(k) which stays
invariable, the refinement of the model also makes the eigenvector o(_~(p, k) invariable. It will
be, as above, determined by eq. (4.1.8).
Substituting eq. (4.2.17) and (4.1.3b) into eq. (4.1.5) for all wave vectors k = k0 entering
the list (4.2.1) and (4.2.2) yields the following results:
(1) The eigenvalues 2(_~(k0) decrease at k 0 = {½1 0}, k0 = {~ 3 ~} and k 0 = t~ ~ ~, by 2W4,
W4 and 3 I414, respectively:

2(-)(ko)ko={½½0~= - 2 W I - 21414
2(-)(ko)k0=~½]~/= -3W~ + 3W2 - W3 - 3W4. (4.2.18)

(2) The eigenvalues 2(_)(ko) at ko = (000) and ko = { 100} increase by the same value equal
to 6W4:
2(_)(k)ko =(ooo)= -6W~ + 12W2 - 8W3 + 6W4
2(_)(k)ko=~too} = - 4 W 2 - [2Wt - 814131 + 6W4. (4.2.19)
(3) The eigenvalues 2(_)(k0) at all remaining wave vectors ko entering the list (4.2.1) and
(4.2.2) either do not change at all or increase.
Since interaction in fourth coordination shell, W4, reduces the eigenvalues at k0 = {I ½0},
k0={~ ~ ~} and ko = {~ g ½}, the minimum eigenvalue falls on the wave vectors of the stars
q} and {~ ~ ½} at certain values of interaction energies W], 1412, W~ and W,. The
diagrams of Fig. 21 confirms this application. It shows that the minimum eigenvalue may be
also realized at k0 = {½½0},ko={~3~ ~ ~} and k0 = {½ ~ ~} as well as at k0 = (000) and k0 = { 100}.
Therefore, the refinement of the interatomic interaction model extends the list of possible
stable superstructures. Compounds generated by the stars {½½0}, {~ 3 ~} and { ~ ~} also prove
to be possible.
Let us analyze structures with a fixed stoichiometry which may be built on the basis of these
additional stars, {I t 0}, {135~
q} and {] ~11}.
4.2.3.1. Stable structures generated by the star {I ½0}. Substituting the vectors of the star
{1 ½0} into eq. (4.1.8) yields
~22(1, 1) at ko = _+(~ ½ 0}, +(0 ~ ½), _+(½ 0 2]-)

D(_)(p, ko) = (4.2.20)
at ko = +(½To},-+(O'T~ 9, --(-~ 0 -~).
--'~¢
q5
bt
FIG. 21. Stability field diagram for the fourth neighbor interaction model indicating the mutual
location of the minimum eigenvalue areas related to k0 = (000), {100}, {~0},
~~ ~35 {~ ~} .
{~vv},
Thus there are twelve concentration waves related to the star {½½0} (their number is equal
to the number of wave vectors figuring in the star {½½0}). As follows from eq. (4.2.20) these
concentration waves have the form:
o(_)(p, k0) ea~k°R= f ~ 2 (1, 1)e a"ko~
L~2(1,-1)ea"t°"
at
at
t,o = +_(½ ½ o), +_(o ½ ½), +_(½o ½)
k0= TO
), IT
(4.2.21)
Utilizing in eq. (2.3.1) the concentration waves (4.2.21), we are able to construct only two
functions n (p, R) assuming on all tetrahedral interstices {p, R } two values, either 1 or 0. The
first function is
1 1F1 --i
n4(p, R ) = ~ + -~L---~ v(_)(p, ko) ea~'°R + ~ 2 o(_)(p, ko)* e-'2~'°t~1
J'½+~[cosn(x+y)+sinlr(x+y)] at p = l
(4.2.22)
=~½+½[coszc(x+y)+sinrr(x+y)] at p = 2
where k0 = (½ ½0). This superstructure has the stoichiometric formula
M[Ol/2 [] 1/2][01/2 [] 1/2]= MO
in the case when O atoms are interstitials.
The second function is generated by all the twelve concentration waves (4.2.21):
1 1 o)
ns(p, R) = -4 + 4 - ~ ~ v(_)(p, k~) exp(iZnk~R)
i (2)
4- --4--w/~w/~~ o(_)(p, k ~) exp( i 2~k 'oR' ) (4.2.23)
where:
(1)
is the sum taken over six wave vectors k;, + (½ ½0), ___(0 ½½), + (½ 0 ½);
k~
(2)
is the sum taken over the remaining wave vectors k~', + (½ ~ 0), +__(0 ½~), + (½ 0 ~).
k~
1
For o(_)(p, k;) = ~ (1, 1) in the first term of eq. (4.2.23), and v(_)(p, k~) = ~ (1, - 1) in
the second term [see eq. (4.2.20)], eq. (4.2.23) may be arranged as
ns(p, R) = 41-4- ¼(1, 1)[cos ~(x + y) 4- cos r~(x + z) 4- cos rc(y + z)]
+ ¼(1, - 1)[sin 7r(x - y) + sin ~ ( - x + z) + sin n(y - z)]
~ + i[cos rc(x + y) + cos g(x + z) + cos r~(y + z) + sin n(x - y)
= +sinrc(-x+z)+sin~(y-z)] if p = l
il + ¼ [ c o s r c ( x + y ) + c o s r c ( x + z ) + c o s r c ( y + z ) - sinrc(x-y)
-sinrc(-x+z)-sinn(y-z)] if p = 2 . (4.2.24)
/7" I-/1 1~2" I./'l~ I.¢"[' !

I ]iTl liTl li
J I/~'1 L/"ql q.,~l ~_.¢ql I/7"
IL,,/T IL/q Ib~r t~ I /
FIG. 22. The superstructure M20 described by the O-atom distribution (4.2.24) in tetrahedral
interstices of the fcc host lattice formed by M atoms. ©, O; O, M.
The oxide described by eq. (4.2.24) has the stoichiometric formula

M[O1/4 []3/4][Ot/4 [] 3/4]= MO1/2 or M20 (4.2.25)
if O atoms are interstitials.
Placing interstitial atoms in interstices {p, R} where ns(p, R ) = 1, we obtain the super-
structures of Fig. 22. Equation (4.2.24) also describes a structure antiisomorphic to that of
Fig. 22. The antiisomorphic structure can be derived from the original structure of Fig. 22
by substituting O-atoms for vacancies [] and vice versa. This procedure leads to the structure
of Fig. 23 and the stoichiometric formula given by the relation
M[ [] 1/4 03/4] [ [] 1/4 03/4] = M03/2 o r M203
which follows from formula (4.2.25). Substituting k~ = (½ ½O) and o(_)(p, k~) = ~ (1, l) and
4z
FIG. 23. The M203 superstructure (Sc203, Y203, In203) antiisomorphic to that depicted in Fig. 22.
0 , M; C), O; 0 , oxygen vacancy.
k0,, = t,i~
I T 0) and o(_)(p, k o,,) = 1 (1, T) into eq. (4.1.17) gives the formfactors lT(k~)) and
lT(k~') of the intracrystalline field to be equal to zero. This field generated by the ordered
distribution of interstitials (4.2.22) and (4.2.24) is homogeneous on fcc host lattice sites.
Therefore the structures presented in Figs 22 and 23 are to be stable with respect to formation
of structural vacancies in the host lattice sites occupied by metal atoms. This means that stable
oxides of the MO, M20 and M203 types generated by the star {½½0} might be expected. In
accordance with this prediction, the oxide M203 of Fig. 23 was really observed in rare-metal
oxides, Sc203, Y203 and In203. (39)
4.2.3.2. Stable structures generated b y t h e star {~ 35}. As was shown at the end of Section
2.4, all multiples of the vector k0 = (~ 35) belong to the same star {135} since multiples
of k0 are
t ~ l~~~,, 4k0 = ~.7
k0 = (7 3 5), 2k0 = (5 -T7~), 3k0 = ,7 t35--T~
7 7/ 5k 0 ~__ (51ff~), 6k0=(~35)
-- -- (4.2.26)
to within a reciprocal lattice vector of the fcc host lattice. This is the reason why a layer
superstructure generated by the set of concentration waves
o(_) ( p, sko ) ex p ( i 2nskoR ) (4.2.27)
where s = 1,2 . . . . . 6 and k0 = (7T ~3 5) nevertheless meets the maximal amplitude principle. For
_
the case where k0 = (~ 3 5), H = (I 3 5) and Sl = 7, the requirement (4.1.12) is met if

( 7r 3zr ~-~) 8 ~ 3n 5re
2Wl c o s - ~ + c o s - f f - + c o s + W3 cos ~ cos -ff- cos -7-- > 0 (4.2.28)
Since c o s ( n / 7 ) + c o s ( 3 n / 7 ) + c o s ( 5 n / 7 ) =½, cos(n/7) cos(3n/7)cos(5rt/7) =~ and by

definition, WI > 14/3, the inequality (4.2.28) always holds. Substituting the wave vectors
(4.2.26) into (4.1.8) and bearing in mind the inequality (4.2.28), provide the same eigenvector
for all wave vectors listed in (4.2.26)
u(_)(p, sko) = ~ (1, 1) at s = 1, 2 . . . . . 6. (4.2.29)
Superposition of concentration waves (4.2.27) with the eigenvectors (4.2.29) yields the
density function
8=6
n6(p, R) = c + ~ ~(_)(sko)o(_)(p, sko) exp(i2rcskoR ). (4.2.30)
Using the eigenvectors (4.2.29) in eq. (4.2.30), we may rewrite the latter in the form
+ ~ , 7(_)(sko) l,-exp(i2rcsko R ) when p = 1

= ,/2
n6(p, R) = ,=6 1
+ ~=,~(_)(sko)--~exp(i2nskoR) when p = 2.
In other words,
a=6 1
n6(1, R) = n6(2, R) = c + ~ y(_)(sko)---~exp(i2rrkosR ) (4.2.31)
s=l x/z
i.e. the function (4.2.31) describes the same distribution of interstitials in the T~ and T:
interstices. In the T~ and T2 fee sublattices interstitial atoms form the same layer super-
structure. The recurrence period (motif) of the superstructure consists of seven alternating
(I35) planes filled with interstitial atoms and vacant.
The maximal amplitude principle by itself does not determine the sequence of filled and
vacant (I35) planes in a structure described by eq. (4.2.31). It is associated with quite an
exceptional situation taking place in this case: the all multiple wave vectors, k0, 2k0 . . . . . 6k0,
prove to belong to the same star {-~3 ~}, and thus all the amplitudes, ~(_)(sko), are dominant
wave amplitudes. In such a situation, the maximal amplitude principle dictates maximizing
the sum of squared moduli of amplitudes,
s=6
i ?(_)(sk0)[2, (4.2.32)
s=l
for the stable sequence of filled and vacant (i35) planes to be determined. However, the sum
(4.2.32) is unambiguously determined by the fraction c of (I35) planes occupied by interstitial
atoms [see the summation rule (2.2.19)] rather than by the succession of filled and vacant
planes. Therefore we face a situation when the pairwise interaction energy is degenerated with
respect to any sequence of filled and vacant planes in a seven-layer superstructure. The
degeneration may, however, be eliminated at a finite temperature when some degree of
disordering occurs. According to Ref. (40), the necessary condition of stability of a
superstructure is the requirement for the moduli of nonzero concentration wave amplitudes
belonging to the same star to be equal to each other. Applying this theorem to the relevant
case gives
Iy~_)(k0)l = 17~_~(2k0)1 . . . . . I w~_)(6k0)l. (4.2.33)
There is the only distribution n6(p, R) assuming two values, either unity or zero, on all
interstices {p, R }. It can be obtained substituting into eq. (4.2.31) the equalities
7~_)(k0) = y~_)(2k0) . . . . . ~_)(6k0) - x/~ (4.2.34)

7
This is consistent with the requirement (4.2.33). The substitution yields
1 2 I- 2n
rt6(1 , R ) = n6(2 , R ) = ~ + - ~ / c o s ~ ( - x + 3y + 5z)
2rt 2rt ]
+ cos -ff (5x - y + 3z) + cos ~- (3x + 5y - z) . (4.2.35)
Placing interstitial atoms into interstices {p, R } in which n6(p, R) = 1 we obtain a seven-layer
superstructure whose stoichiometric formula is
M[OI/7 [ ] 6/7][O1/7 [ ] 6/7] = MO2/7 or M702 (4.2.36)
if O atoms are interstitials. The metal atom valency consistent with the stoichiometric formula
(4.2.36) is ~ < 1. As the valency of any metal is larger than unity, the oxide M702 cannot exist.
The distribution function (4.2.35) may however describe an antiisomorphic structure of
n6(p, R), which is regarded as the density function of interstitial atom vacancies rather than
interstitial atoms. Then, to obtain the antiisomorphic structure, we should introduce
interstitial atom vacancies into interstices {p, R } where n6(p, R ) = 1 and interstitial atoms
into interstices where n 6(p, R ) --- 0. The stoichiometric formula may easily be obtained from
(4.2.36) by substituting O for [] and [] for O. It yields
M [ [ ] 1/7 O6/7][['~ 1/7 06/7] = MO12/7 or M7012 (4.2.37)
The antiisomorphic structure M7012is generated by the same sequence of filled and vacant
(I35) planes drawn in the Tl and T2 fcc sublattices of tetrahedral interstices. This sequence
may be presented as follows:
...~OOOOOOIk-]OOOOOO[]O... (4.2.38)
The metal atom valency consistent with the stoichiometric formula (4.2.37) is ~. Since we
here consider oxides with a fixed metal valency, the fractional valency ~ = 33 cannot occur
unless the fcc host lattice is occupied by two or more types of metal atoms with different
valencies. The stoichiometric formula of such oxides may be derived from (4.2.37). It has the
following form
(M', M"...)[Ik-] 1/7 O6/7][ [] 1/7 0 6 / 7 ] = (M', M",...)O12/7 (4.2.39a)
or
(M', M " , . . . ) 7 O12. (4.2.39b)
Let us consider the case when the host lattice is occupied by metal atoms of two types. To
ensure a mean valency equal to 33, one constituent should be of valency Z ' = + 3 and the
other constituent should be of valency, Z", which is larger than + 3; in other words Z " may
be equal to 4, 5 or 6.
In the case of Z ' = 3 and Z " = 4, the stoichiometric formula (4.2.38) fitting these valencies
is
+3 M3/7
(M4/7 +4)012/7 or M+3 M~-4 012 (4.2.40)
In the case Z ' = + 3 and Z " = + 5 the stoichiometric formula is
+3 +5
(M~ M~ )O12/7
This formula cannot, however, be realized since it may fit only a superstructure whose
recurrence period consists of fourteen rather than seven (I35) planes as required. In the case
of Z ' = + 3 and Z " = + 6 the stoichiometric formula is
(M 6~73MI/7
+6)O12/7 or M~-3 M +6 O12 (4.2.41)
This analysis shows that the stoichiometric formula of only two oxides, M2"3 M; -4 O12 and
M +3 M +6 O12, generated by the star {1 3 5} are consistent with the valency of constituents. The
distribution of two metal constituents over fcc host lattice sites can be easily found if the
interchange energy between metal atoms is assumed to be much smaller than the interaction
energy between interstitial atoms.* In this case the distribution of metal atoms is determined
by the modulation of the intracrystaUine field generated by interstitials along host lattice sites.
Let us find the intracrystalline field ~u(R). Since all multiples of the wave vector k 0 = (T 3 5)
belong to the same star {~3~}, the formfactors of the intracrystalline field, V(k0),
I7(2k0) . . . . . 17(6k0), are equal. Substituting the wave vectors (4.2.26) and eigenvectors
(4.2.29) of the dominant waves into (4.1.17) yields for these formfactors the following values:
8W0 . ~ 3x. 5x 1
17(ko) = 17(2ko) = . . . = 17(6k°) = ~,,/2 sm --14sin - ~ s i n 14
- - = -~/2
- = Wo (4.2.42)
*By definition,the interchangeenergyis Bz~t(R) = WM,M,(R) + WMOM.(R) -- 2WM,M,(R) where WM,M,, WM,u,,and
WM,M-are interaction energies of M'-M', M"-M" and M'-M" pairs.
J,P.M.S, 29/1-2--G
since
n 3 n . 5n 1
sin -i4 sin -i4 sm -i4 = 8"
As the distribution function for interstitial atoms in the antiisomorphic structure is

n~nt(p, R) = l -- n6(p, R)
where nr(p, R) is given by eq. (4.2.35), the definition (4.2.30) yields
)~ant
<-)t[ S k 0)X = -r~_)(sko) (4.2.43)
Substituting (4.2.42), (4.2.43) and (4.2.26) in (4.1.13), we obtain the equation for the
intracrystalline field on the fcc host lattice sites of {R }:
~(R) = ~0+ cos--~- ( - x + 3y + 5 z ) + c o s , (5x - y + 3z)
+ c o s ~ - ( 3 x + 5y - z ) -~W0. (4.2.44)
One may readily see that the potential (4.2.44) assumes only two values on host lattice sites,
~'/1 ~ ~'J0 + ~W0 and ~ = 7 ' 0 - ~W0. Since the interaction energy between the nearest metal
and oxygen atoms is negative (metal and oxygen atoms attract each other because they are
ions having the charges of opposite signs), the minima of the field (4.2.44), ~P~, fall on each
seventh plane (I35). The maxima of the field, ~z, fall on the remaining (i35) planes. To
provide the minimum of the interaction energy of anions and cations, the metal ions with
larger valency should be placed in the minima of the field, ~ ( R ) , i.e. in each seventh (I35)
plane drawn in the fcc host lattice. For the oxide, M~-3M+6OI2, this procedure gives the
following sequence:
... M+3M+6M+3M+3M +3M+3M+3M+3M+6M +3 .... (4.2.45)
Let us introduce a specific graphic form which would lead to a simple description of the
entire structure including the mutual location of host atom and interstitial atom sequences.
To do it, we should introduce a unit element of the structure so that any layer interstitial
structure might be represented as a succession of these unit elements filled with metal atoms
and interstices in various fashions. In the associated case the unit element is a "molecule"
consisting of a (I35) plane of the host lattice and two nearest (I35) planes in the T~ and T2
sublattices of tetrahedral interstices shifted with respect to the initial (I35) host lattice plane
1 + a2 + a3) and -~(at
by the distances, ~(al 1 + a2 + a3), respectively. Let the graphic image of
such a unit element be
where the circle designates the (i35) host lattice plane, the upper and bottom squares
designate the nearest (I35) planes in the T~ and Tz tetrahedral sublattices, respectively. The
,1£/1
FIG. 24. The component of the layer superstructure M+6M~3012 where' the sequence of metal and
oxygen atoms is described by (4.2.46). ~ , M+6; C), M+3; O, O; I-7, oxygen vacancy.
location of the metal atoms sequence (4.2.45) and oxygen atoms sequence (4.2.38) with respect
to each other in the M + 3 M + 6 0 1 2 oxide may then be represented as follows:
(4.2.46)
where the squares [($35) planes of tetrahedral interstices] are filled either with O atoms, or
with their vacancies, [ ] , and the circles [(T35) planes of host lattice sites] are filled either with
M +6 ions or M +3 ions. This structure is shown in Fig. 24. As for the structure of the second
oxide, M~-3M f 4 O12, each seventh (T35) plane of the host fcc lattice should be filled with M +4
atoms. The remaining six (T35) planes of the motif should then be randomly occupied by M +4
and M +3 atoms with equal probabilities.* The mutual location of the metal atom sequence
and oxygen atom sequences then have the form:
(4.2.47)
The shaded circle equals ~M
~ +4 + ~M
1 +3 and designates a (T35) host plane randomly occupied
by M +4 and M +3 atoms with equal probability. This structure is shown in Fig. 25. The
structures of oxides M~M"O12 and M~M['O~2 derived above from the theoretical standpoint
have been observed. These structures describe frequently occurring rare-earth metal oxides.
For illustration, the compounds M 6 M ' O t 2 and M4M~O~2 are shown in Table 3.
*This conclusion does not, however, hold if the interaction energy of M + 3-M + 4, M + 3-M + 3 and M ÷ 4-M + 4
pairs is incorporated into the model.
.,4 _A
.,'I" ; L/TI L,,k,'~

.A
l/" 9"
Fit3. 25. The component of the layer superstructure M4M~O~2 where the sequence of metal and
oxygen atoms is described by (4.2.47). ~ , M'; ~, ~M + 2 M'; O, O; [-], oxygen vacancy.
4.2.3.3. Oxides generated by the star {½5½}. It follows from eq. (4.1.8) that at k0 = (½11~7)
o(_)(p, k0) = - ~ ( 1 , 1) (4.2.48)

% ,
The corresponding dominant wave is
o(_)(p, ko) exp(i2rckoR) = 3 (1, 1) exp~t-~-

/ . 2x (x + y + z ) ) (4.2.49)
The dominant wave (4.2.49) and the conjugated wave o~_)(p, k0)* e -a~k°R generate the only
function (2.3.1) which is either 1 or 0 on all interstices {p, R}:
n7(p,R ) = ~ + ~-~o(_)(p, k0)e a~'0R+ Tx/~v <-)(P' k°) ea~k°R

1 2 2rt
-5+~cos-~-(x+y+z) at p = l
= (4.2.50)
1 2 27r
-~+~cos-~(x+y+z) at p=2
Since the first term of (4.2.50) is ½, it describes the fraction of occupied (111) planes drawn
in the T 1 and "1"2sublattices respectively, and the stoichiometric formula of the oxide described
by eq. (4.2.50) is
M[OI/3 [ ] 2/3][O1/3 [] 2/3] = MO2/3 or M3 02 (4.2.51)
The oxide M302 may arise at a metal valency equal to 4/3. This valency is consistent with
the stoichiometric formula
(M~/31M 1/31[L11/3
+2xr,', [] 2/3][O1/3 [ ] 2/3] or M +2 M~-1 O2 (4.2.52)
which may be realized for the mixture of monovalent metal M +1 and divalent metal M +2 in
the host lattices.
Table 3. Typical Oxides M7012 with the

Structure Described by eq. (4.2.35)
Oxides Literature
U R 6 0 | 2 , R = La-Lu and Y (41)
WR6Ot2, R = Gd-Lu, Y (42)
MoR6OI2, R = Er-Lu, Sc. (43)
Sc4Ti3Ot2 (44)
Sc4Zr3Ol2 (45)
Sc4Hf3012 (46)
Yb4Zr3Ol2 (45)
Er4Zr3Oi2 (45)
Tm4Zr3Oi2 (45)
Lu4Zr3012 (47)
Pr7012 (48)
Ce7012 (49)
I"o7012 (50)
Mg2ZrsO12 (51)
Mg2HfsOi2 (51)
The stoichiometric formula of the antiisomorphic superstructure can be obtained by

substituting [] for O and O for [] in (4.2.51):
M[[~ 1/3 O2/3][[~] 1/3 02/3] = MO4/3 o r M 3 04
The oxide M 304 may arise at metal valency equal to 8/3. This valency is consistent with the
stoichiometric formula
(M~32 M~/3)[ [] 1/3O2/3][[] ~/302/3] = M~-~2 M2~3 04/3 or M +2 M f 3 04 (4.2.53)
which may be realized for a mixture of divalent and trivalent metals in the host lattice. To
our knowledge, the oxides, M~M'O2 and M'M~O4, have never been observed. They may
however serve as primary superstructures for the secondary superstructures.
4.2.4. Conclusion
Summing up this section, the structure of almost all known binary oxides with a fixed
stoichiometry based on occupancy of tetrahedral interstices of the fcc host lattice were
predicted within the framework of a simple short-range interaction model applying maximal
amplitude principle. We derived the sphalerite structure (ZnS, ZnO) generated by the (000)
star, the structures of oxides, CuO, PtO, PdO, Cu203, A1203, As203, Sb203, 6-Bi203, PbO and
SnO, generated by the {100} star, the structures of ScaO3, Y203 and In203 generated by the
{½½0}, and the structures of the type of Y6UO12 and Sc4Ti3Ol2 generated by the {½3 5} star.
The proposed approach also enables us to determine the stability ranges where each of the
structures may be formed. In the framework of the fourth coordination shell interaction
model, the stability fields are shown in Fig. 21.
4.3. Secondary Interstitial Superstructures in Tetrahedral Interstices of the fcc Host

Lattice
The superstructures considered above have a fixed composition meeting the classical
valency rule. In what follows, the widespread particular case when the composition of the
primary superstructure deviates from that dictated by the valency rule will be discussed. To
maintain the agreement between the valency of constituents and stoichiometric composition,
we must remove some of the atoms from the primary superstructure and thus obtain
structural vacancies. Secondary ordering of structural vacancies over "permitted" sites of the
primary nonstoichiometric superstructure may reduce the configurational interatomic inter-
action energy. This process leads to the formation of a secondary superstructure. Applying
the maximal amplitude principle to the nonstoichiometric primary superstructures will give
us the most stable secondary superstructures.
4.3.1. The characteristic matrix

As in the case of the secondary ordering based on the bcc host lattice, we shall begin with
the construction of the characteristic matrix ~pq(k) defined on "permitted" tetrahedral
interstices according to the equation
Vpq(k ) = ~ Wpq(r ) e x p ( - i2rckr ) (4.3.1)
where the tetrahedral interstices (p, 0) and (q, r) are "permitted" in the primary super-
structure, and the summation is performed over all "permitted" fcc lattice sites {r }.* In the
case of two crystallographically equivalent tetrahedral sublattices, we have
9pq(k)=(V_l,(k) V,2(k)~ (4.3.2)
\V*(k) 9,~(k)]"
The lower branch of the eigenvalue spectrum of the matrix (4.3.2) is
~_)(k) = ~ , ( k ) - [ ~z(k)l. (4.3.3)
Its eigenvector is
~*2(k)
5,_,(p,k)=(1, [ ~,2(k) i ) . (4.3.4)
The characteristic matrix Vpq(k) defined on "permitted" interstices {p, r} can be conveniently
expressed in terms of the matrix Vpq(k) defined on all T1 and T~ interstices of the original
fcc host lattice. To do this, we may rewrite eq. (4.3.1) in the equivalent form
~pq(k ) = ~', Wpq(R)n ~O)(p,R) e x p ( - i2nkR ) (4.3.5)

R
where n~°)(p,R) is the distribution function of the primary superstructure equal to unity at
"permitted" sites, R = r, and to zero at "forbidden" sites, R ¢ r. The "weight function"
n~°)(p,R) in the summation in eq. (4.3.5) controls excluding "forbidden" sites R ¢ r from the
sum (4.3.5).
Let the function n~°)(p,R) have the form
n~°)(p,R) = Co+ ~ ~l°)_)(kj)vl~)(p,kj) exp(iZTrkjR ) (4.3.6)
J
where kj are wave vectors of the dominant waves generating the primary superstructure.
Substitution of (4.3.6) into (4.3.5) yields
~Tpq(k)= gpq(O)c 0 -Jr-~ gpq(k - kj)7l_)(

o) k j) o I-)(P,
o) kj) (4.3.7)
)
*Equation (4.3.1) holds if "permitted" sites form a Bravais lattice. This is the case with all the primary
superstructures under consideration.
4.3.2. Secondary superstructures based on the primary superstructures of the CuO and PbO
types generated by the star { 100}
(a) Let us consider secondary ordering occurring on the basis of the CuO-type primary
superstructure with the stoichiometric formula
M[Ol/2 [] 1/2][01/: [] 1/2]
described by the distribution (4.2.9).
Comparing eqs (4.2.9) and (4.3.6), one may see that
1 1
Co=½, yl°_))(ko)=w/~, o/°_))(p,k o ) = ~ ( 1 , 1 ) and ko=(O01 ) (4.3.8/
Substituting (4.3.8) into (4.3.7) results in
Vii(k) = Vll(k ~2 --F Vll(k - ko) ~ 1 1 = ½[Vn(k) + Vn(k - ko)] (4.3.9a)
1 1
~2(k) = V~2(k~+ V12(k - k0) x/~ x/~ = l[Vlz(k) + V~2(k- ko)] (4.3.9b)
Making use of (4.1.3) and (4.2.17) in (4.3.9) gives

Vii(k) = 4 WECOSnkx COSnky + 2 W4[cos 2nkx + cos 2nky + cos 2nk~] (4.3.10a)
Vl2(k) = [2 Wl COSnk~ + 8 W3 cos nkx cos nky cos nkz]ein(kx+ ICy + kz) (4.3.10b)
Equation (4.3.3) with a matrix elements (4.3.10) reads
2(_)(k) = 414"2cos nkx cos nky + 2 W4[cos 2rCkx+ cos 2rcky+ cos 2nk~]
-[2Wlcosnk~+8W3cosnk~cosxkycosnk~l (4.3.111
The primary superstructure determined by eq. (4.2.9) occurs in the case when W3/W~ < ¼and
2(_)(k) given by eq. (4.1.5) assumes its minimum value at k = {100}. In this case the
eigenvalue ](_)(k), as follows from eq. (4.3.11), assumes the minimum value at
k=k~=(lO0) and k=k~=(OlO).

According to eq. (4.3.4) and (4.3.10), the associated dominant waves are
r,, k,,e,2,k~'= 1 ( 1 , 1 ) e a , , ~ , = l ( 1 , 1 ) e , 2 ~ = 1 (1,1) exp(i2nx)
-6,_)(p, k~)e'2~'~"= ~ (1,1)e'2~*~'=~ (1,1)ea" = ~ (1,1)exp(i2~y). (4.3.12)
The occurrence of complementary concentration waves (4.3.12) in the primary superstructure

(4.2.9) leads to the distribution (4.2.10) discussed above.
(b) Let us consider secondary superstructures based on the primary superstructure of
PbO-type described by eq. (4.2.16). This primary superstructure occurs at
W3 > 1
Wl 4"
.104 PROGRESS IN MATERIALS SCIENCE
Comparing eqs (4.2.16) and (4.3.6) one may see that in this case
~,(o) t k,,,~
Co= l , ~(_), oj=~, 1 ,o) . . . . .K. o~) = ~ ( l1 , i )
v/_)tp, and ko"=(001) (4.3.13)
Substituting eq. (4.3.13) into (4.3.7) yields

,,, 1 l
Pl,(k) = V.(k)½ + V . ( k - k o = ½[V.(k) + V,,(k -
,, 1 1
fft2(k) = Vt2(k) ) - V12(k - ko ) ~ - ~ - ~ = ½[V12(k) - Vz2(k - k~")]. (4.3.14)
Making use of (4.1.3) and (4.2.17) in (4.3.14) yields

1711(k) = 4 W 2 c o s ~zkx c o s nky + 2 W4[cos 2nkx + c o s 2nky + c o s 2nkj
1712(k) = 2 W1[cos nkx + cos nky] exp (in (kx + ky + k~)). (4.3.15)
Equation (4.3.3) with (4.3.15) reads
;[(_)(k) = 4W2 cos nkx cos nk~ + 2 W4[cos 2nkx + cos 2nky + cos 2nkA
- 12Wt[cos nkx + cos nk~] 1. (4.3.16)
The primary superstructure determined by eq. (4.2.16) arises in the case
W,>l
W1 4"
In this case the minimum of 2(_)(k) given by eq. (4.3.16) again falls on the points
k=k~=(lO0) and k=k'o'=(OlO). (4.3.17)
Following eq. (4.3.4) and (4.3.15), we have
6 (_)(p, ko)
' = -o(_)(p, k "0) = - ~ (1, -- 1). (4.3.18)
The complementary waves with kl = k ~ = (100) and k~ =k~'--(010) and "polarization

vectors" (4.3.18) in the primary superstructure of (4.2.16) yield the distribution which is
antiisomorphic (4.2.10) and thus does not result in a new superstructure.
4.3.3. Secondary superstructures based on the primary Cu20-type superstructure generated by
the star { 100} (pyrochlore, sheelite)
Unlike the above cases, the new secondary superstructures arise on the basis of the primary
superstructure
M [ O I / 4 [ ] 3/4] [O1/4 [ ] 3/4]
described by the distribution (4.2.10). This primary superstructure is characterized by the

following values
0) k ' -- o) ,t 4,(0) tl.."t 1
t" (-)~,~'0 I -----
- = 2v/
ol°)_)(p, k~) = ol°)_)(p, k'~) = ol°)_)(p, k6") = ~ (1, 1), Co= ¼ (4.3.19)
w
obtained by comparison of eqs (4.2.10) and (4.3.6).


1 1 1 1 1 1
17,1(k) = ¼VH(k) + VH(k - k~) 2,/2v -, ,/ ~ ~- VH(k - kg) 2x/~x/~2 2 ~- ZH(k - k~') 2x/~x/~
=¼[v.(k) + v.(k - k~) + v . ( k - k~') + v . ( k - kg')]

1 1 1 1 1 1
V , ~ ( k ) = ¼v ,~ ( k) + v,2(k - k~) - -
= ¼ [ v , ~ ( k ) + v , : ( k - k ; ) + v,2(t~ - k~') + v,~(t, - t~;")]. (4.3.20)

Substituting eqs (4.2.17) and (4.1.3) into (4.3.20) leads to
iTll(k) = 2 W4[cos 2nk, + cos 2rcky + cos 2nkz]
1712(k) = 8W 3 cos nkxcos ~kr cos rtk, exp(iTt (k~ + ky + k,)). (4.3.21)
Equation (4.3.11) with (4.3.21) yields
:;[<_)(k) = 2 W4[cos 2nk~ + cos 2nky + cos 2nk~] - 8 W3 [ cos nkx cos rcky cos rckz I (4.3.22)
The indices (HxHyHz) of the reciprocal lattice vectors H of the relevant primary super-
structure run over all possible integers since the primary superstructure has a primitive cubic
lattice. As shown in Section 2.4, stable superstructures with fixed stoichiometries are
generated by dominant concentration waves with wave vectors
H
k~=-- where s~=2,3,4.
$1
Reducing all such vectors into the first Brillouin zone of the primary superstructure
(the Brillouin zone of the primitive cubic lattice), we obtain a finite series of possible wave
vectors k~:
{k,} = o o}, o o}, {¼ o o}, {½ ½o}, o}, {¼ ¼o}, {½ ½½}, i},
{¼¼¼}, {½¼0}, {½¼¼}, {½½¼} (4.3.23)
Substituting the wave vectors (4.3.23) into (4.3.22) and comparing the resultant eigenvalues,
one may see that the lowest eigenvalue ~[(_)(kl) is attained at
4
k~ --- {1 ½½} if ~ W3 < I414 (4.3.24)
~,/e
and at
kl={¼00} if W4
< 45x/~W3~0.565W3 (4.3.25)
Let us consider what the secondary superstructure is when the relation between interaction
energies is (4.3.24). In this case the star {½1½,} of the__dominant waves consists only of
the vector kl = (½ ½½) [all other vectors of type (½ ~~ ~),(½1
l I
~) etc. differ from the (~i ~i 2)
1
vector
by a reciprocal lattice vector of the primary superstructure]. Substitution of k = k~ = (½ 1 ½)
into (4.3.21) yields V12(ki)= 0.
The latter conclusion follows from the symmetry of the system rather than from the
short-range interaction approximation (4.1.2) used above. Since Vl2(k~) = 0, the matrix (4.3.2)
is degenerate, i.e. both eigenvectors
= (1, 1) (4.3.26a)
and
~(_)(p, kl) = ~ 1 ( 1, - 1) (4.3.26b)
are related to the same eigenvalue ]~±)(kl)= Fil(kl).

The related wave corresponding to the eigenvectors (4.3.26) is
~±)(p, k0 e t2 nk l r = ~ 1 (1, + 1) e '~"kt'. (4.3.27)
Equation (2.3.1) for the stable atomic distribution thus has the form
nl~)( p, r) = c + 7(kl)o~±)(P, kO exp(i27tklr)
1
½c +e(±)(kO----~exp(i2nklr) at p = 1
,/2
= .i
(4.3.28)
½c +y(±)(kO~-~exp(i27~klr) at p =2.
x/-
At c = 1 and ),~_)(kl)= 1/x/~ the function (4.3.28) takes only two values on "permitted"
interstices {p, r}, either unity or zero. The function (4.3.28) may then be rewritten as
nl~)( p, r) = 5½~+ ½~exp(i2nklr) at p = 1 (4.3.29)

~5+5exp(i2nklr) at p = 2 .
To rewrite the distribution (4.3.29) in terms of arbitrary fcc host lattice sites, {R}, i.e. to
introduce the host lattice sites, {R}, instead of the "permitted" sites, {r}, of the primary
superstructure, eq. (4.3.29) should be rewritten as
n~(p,R)=n2(p,R)nl~)(p,R)=~nl~)(p,r) if R=r (4.3.30)

( o if RCr.
Equation (4.3.30) holds because, by the definition of the permitted interstices, n2(p, R) = 1
at "permitted" interstices (where R = r), and n2(p, R) = 0 at all other "forbidden" interstices
(where R ¢ r). Substituting (4.2.10) and (4.3.29) into (4.3.30) at k 1 = (1 I 5)
1 and R = (x, y, z)
yields
1 i2nx ,2ny f2nz 1 +lein(x+y+z)]
_.)'[¼+z(e )][~ +e +e at p = l (4.3.31a)
n+(p,R)=([4+7,(el ,2,~ +e'2"Y +e'2"~)][~½e,,t~+y+~)]~
+ ' at p = 2 .
Performing the multiplications in (4.3.31a), we have
n~(1, R) 8- , !e8 -_a_!t ,2~ + e '2ny+ e '2"z) "k- t[ein(x+Y+Z)q-ein(-x+Y+Z) -+- e in(x-y+z) + ein(x+y-z)].
n~±)(2, R) - 8 1+ 8 (1e - ,2,x.+_ ei2ny+ e,2,~)
_+ l[e~(x+Y+~)+e~"(-~+Y+Z) + e ~"(~-y+z) + e;"(~+Y-~)]. (4.3.31b)
It is worthwhile to notice that the distributions nl-)(p, R) and nl+)(p, R) describe two
interstitial atom lattices which are indistinguishable without the host lattice to be taken into
account [as follows from (4.3.31b) nl+)(p, R) =- nl-)(p, R + a0].
Since the configuration energy is assumed to be dependent only on the mutual location of
interstitial atoms, both distributions n ~±)(p, R) describe the superstructures whose interaction
energies (and therefore stabilities) are the same. The latter result could be also readily
predicted from the starting p o i n t of the present consideration. It follows from the fact that
i?~2(kj) = 0 at kj = {½ ½½} and the matrix lT~(kj) is degenerate with respect to two eigen-
vectors, ~(±)(p, kj) and ~(_)(p, ki) which produce the distributions nI+)(p, R) and n[-)(p, R),
respectively.
However, if the host lattice is taken into account, the situation looks quite different: the
distinction between the superstructures produced by both distributions (4.3.31 b) can be easily
made. The superstructure related to n[+)(p, R) corresponds to a cubic phase, whereas the
other related to n[-)(p, R) corresponds to a tetragonal phase.
To make this point more clear, let us consider the intracrystalline field generated by the
distributions of interstitial atoms on the host lattice sites.
As follows from eq. (4.3.31), the distribution function n[±)(p, R) is generated by two stars,
~.100} and {½½½}. Equation (4.1.17) requires that the formfactor of the intracrystalline field,
V(k) vanishes at k = {100}. This signifies that the concentration waves generated by the
star {100} do not make any contribution to the intracrystalline field ~v(±)(R). The entire
contribution to the field is made by the star {½½21-}.
Let us calculate the formfactor ~ ( k ) at wave vectors of the star {½½½}:
kl = (½ t ~),
i (iT iI :,,
1~ I'! ~ 1
,: : ~), (i1 ½--½) (4.3.32)
Substitution of the wave vectors (4.3.32) into (4.1.16) results in
~ f-2W0 at k~=(½½½)
I'Vl(kl)-~- W 2 ( k l ) = ~ 1_] /,1_ ]" 1] 1 (4.3.33)
2Wo at k~=(~½2},~22~,,(~½~ ).
Equation (4.1.13) for the intracrystalline field may be rewritten as
= + e':',"t#,(kj)r (%)o<±)(1, kj) + kj)]

J
= ~Po+ 2 erZ"ijR[l~/l(kj)a(±)(1, kj) + l~:(kj)a(:L)(2, kj)] (4.3.34)
J
where
a(:~)(p, kj) = V(kj)v<±)(p, kj), p = 1, 2,
are Fourier coefficients a (p, k) of the series (1.1.1). Since #1 (k0) -- #2(ko) = 0 at k0 = { 100},
the sum in eq. (4.3.34) includes only four waves with wave vectors of the {½½½} star. As
follows from eq. (4.3.31b), at kj={½ ~} all Fourier coefficients a(±)(l,kj)=~ 1 and
a~±)(2, k j ) = +~. Substituting these values of a<±)(p, kj) into eq. (4.3.34) we have
7t(+)(R) = !tto + ~ e'2~kJ~[I~'l(kj)a<+)(1,kj) 4- I~V2(kj)a<±)(2,kj)]
I11
= tlto 4- ~ E e':'~kJR[[~/l(kJ)4- l/[":(kj)] (4.3.35)

~(_)(R) = ~Po (4.3.36)
1
i.e. the eigenvector ~< )(p, k0 =/ ,-~- = (1, - 1) generates the interstitial secondary superstructure
n[-)(p, R") w h ic h pro d uces th e h~m
omogenousin t racrys t a 11ine f iel d a 1ong t he ficc host "lattice. As
"
1
for the eigenvector 3t+)(p, k~)=---~ (1, 1), it generates the superstructure n~a+)(p,R) which
v-
produces the heterogenous field ~+)(R) along the host lattice.
Making use of eq. (4.3.33) in (4.3.35), we obtain
W0 •
I/J(+)(R) -----~tr/0+ 4 [ - e ' n ( x + y + z) + e ' n ( - x + y + z) + ein(x - y + z) + e irt(x + y - z)] (4.3.37)
The field (4.3.37) takes only two values on all fcc host lattice sites, either
~v0-½W0 or ~0+½W0. (4.3.38)
Since the intracrystalline field ~+)(R) assumes two values on host lattice sites, these sites
cannot be occupied by a single set of atoms otherwise these atoms would have different
chemical potentials and thus could not meet the requirement of thermodynamic equilibrium.
This result leads us to the conclusion that the host lattice cannot be occupied by anions
because the oxides under consideration do not have two kinds of anions to build the host
lattice. In principle, the alternative case when the nonequivalent host lattice sites are occupied
by O atoms and O atom vacancies is also possible. But it may be expected only in quite
exceptional cases since it results in the formation of very loose structures. Therefore, the host
lattice of dense oxides described by the distribution n I÷)(p, R) consists of two kinds of cations,
M and M'.
4.3.3.1. Pyrochlore-type structure. Let us find the stoichiometric formula corresponding to the
distribution (4.3.31 b) for n ~+)(p, R). Since the first term of the right-hand side of eq. (4.3.31 b),
which is equal to ~, is the fraction of sites of the T1 and T2 sublattices, respectively, occupied
by O atoms, the stoichiometric formula of the oxide described by eq. (4.3.31b) is
(M,M')[OI/sIk-I7/s][Ol/sI~7/s]=(M,M')OI/4 or (M,M')40. (4.3.39)
This stoichiometric formula may be provided only by metals with the valency per lattice site
equal to ½. A valency less than unity cannot be realized and therefore an oxide (M, M')40
cannot exist. As for the antiisomorphic structure where n~+)(p, R) describes the distribution
of interstitial vacancies, whereas the function 1-n~÷)(p,R) describes the distribution
interstitial atoms, its stoichiometric formula may be obtained from (4.3.39) by substituting
O atoms for vacancies [] and vice versa. Such substitution in (4.3.39) results in
(M, M ' ) [ [ ] 1/807/8][[] 1/807/8] ~---(M, M')O7/4 or (M, M/)407 . (4.3.40)
In an oxide (M, M')407 the metal atom valency must be equal to 7. Such a valency per fcc
host lattice site is out of the question unless the fcc host lattice is occupied by metal of two
or more types with different valencies. For example, this may occur if the fcc lattice is
occupied by a 1:1 mixture of trivalent and tetravalent atoms. In this case formula (4.3.40)
may be rewritten as
+3 +4
(Ml/2 Ml/2)[ [] 1/807/8] [ [ ] 1]8O7/8] or Mf3Mf407 . (4.3.41)
To find the distribution of trivalent and tetravalent metal atoms along the fcc host lattice we
should again analyze the intracrystalline field on host lattice sites produced by an ordered
distribution of interstitial O atoms.
Because the interstitial atom distribution in the antiisomorphic structure is
n~+)(p, R) ant= 1 -- nl+)(p, R),
their Fourier coefficients are related by the equation

a(+)(p, k) ant = -- a<+)(p, k). (4.3.42)
Using (4.3.42) in (4.3.35) we may rewrite (4.3.37) as
~(+)(R) ant = ~P0- ¼Wo[ -ein(x+y+z) --F e in(-x+y+z) at- e in(x-y+z) -.[-eintx+Y+Z)]. (4.3.43)
Let us introduce a density function ns(R) which is equal to unity at host lattice sites where
~(R) = ~0-~W ~ 0 and to zero at sites where q J ( R ) = ~v0 + 1W0. Such a function may be
represented as
ns(R ) = 1 q.. 41_{_ein(x+y+z) --b e in(-x+y+z) q-- e 'n(x-y +z) + ein(x+Y-Z)}. (4.3.44)
The interaction between the nearest anion host atom and cation interstitial atom is attractive
and thus the interaction energy W0 is negative. Consequently,
'0-½w0= Wol
is the maximum value, and
½w0-- '0-½1 w01
is the minimum value of the intracrystalline field along the fcc host lattice. In this
situation the anion-cation interaction energy assumes the minimum value when cations
with a higher charge, M', occupy host lattice sites where the intracrystalline field ~(+)(R) a"t
takes on the minimum value, ~ 0 - ½ [ W0l, whereas cations with a lower charge atom,
M, occupy the remaining host lattice sites where ~(+)(R) ant takes on the maximum
value, ~o + ½lW01 • Therefore, the function (4.3.44) which is equal to unity at fcc lattice
sites where !P(+)(R)~"t= ~ o - ½ W o = ~0+½1 w01 and equal to zero at sites where
~P(+)(R)a"t = ~P0 + ½W0 = ~0 - ½1 W01 describes the lower charge atom distribution, i.e.
n(M, R) = ns(R).
The function 1 - n s ( R ) thus describes the tetravalent atom distribution, i.e.
n(M', R) = 1 - ns(R)
The structure of the oxide M2 M~ 07 may therefore be obtained if O atoms are placed in
tetrahedral interstices where n[+)(p, R ) = 1 - nl+)(p, R ) is equal to unity, M atoms in fcc host
lattice sites where n s ( R ) = 1, and M' atoms in the remaining fcc host lattice sites. This
structure, displayed in Fig. 26 and formed by combined ordering of O atoms, trivalent and
tetravalent metal atoms is referred to as pyrochlore. This name emphasizes that they are
isostructural with the mineral known as pyrochlore.
The stoichiometric formula of pyrochlore is in fact determined by eq. (4.3.41):
(Lnl/2M~/2) [[]]1807/~][[] l/sO7ts] or Ln2M~O 7
where M' atoms belong to the IV group of the periodical table of element (Ti, Zn, Zr, Hf)
and the symbol Ln denotes a rare-earth element.*
4.3.3.2. Crystobalite structure. There are many oxides besides pyrochlores where the atomic
pattern in "isomorphic" with the pyrochlore structure. One example of this is the cubic
*In the case of the pyrochlore structure, M ~= Ti, Zn, Zr, Hf are higher charge atoms and Ln are lower charge
atoms.
liT iZl
I ./'1"I I/-'TI Xl..-'TI _zdl L/I
I~ 12:/I II/"- l.L.-d
T lIT L ±TI_I
I ~I I~I JJ[/"l .LJ
FIG. 26. The pyrochlore-type secondary fcc-based superstructure, M2M~O 7. Distribution of vacancies
in tetrahedral interstices is described by (4.3.31b), distribution of M and M' atoms in the fcc host
lattice by (4.3,41), (a) Schematic drawing of the pyroehlore unit cell composed of 8 host lattice face
centered cubes belonging to two different types. (b) Shows these host lattice cubes composed of M
and M' metal atoms and filled by interstitial O atoms in different manners. Small open circles
show oxygen vacancies. Oxygen atoms occupying the remaining tetrahedral sites (centers of
½atee × {alee x ½arc¢ small cubes) are not shown. Large filled circles = M; small filled circles = M'.
polymorph of cristobalite, SiO2, where the fcc lattice is occupied by O atoms and structural
vacancies, O atoms being distributed according to eq. (4.3.41). Si atoms are distributed over
tetrahedral interstices in accordance with the distribution (4.3.31b) for n~+)(p,R), i.e. they
occupy the same interstices as oxygen vacancies, ~q, do in the pyrochlore structure. We may
therefore derive the stoichiometric formula for cristobalite from (4.3.41). It is
(OwzF-'lw2)[Sil/s []7ts][Sil/8 [ ] 7ls] = Oj/2Sii/4 o r S i O 2. (4.3.45)
Si atoms in the cristobalite structure occupy centers of tetrahedrons composed of O atoms,
and each O atom is linked with two nearest Si atoms forming a "dumbbell".
Cubic cristobalite is just the exceptional case of a loosely packed oxide which was
mentioned above. In spite of the fact that the intracrystalline field ~(+)(R) assumes two values
on host lattice sites occupied by O atoms, it does not break the thermodynamic equilibrium
between O atoms in the host lattice since O atoms occupy the minima of 'P(+)(R) whereas
the maxima of ~(+)(R) are vacant. In this situation the chemical potential of O atoms assumes
the sole value.
Such a loose structure can exist only because of very strong covalent binding in the SiO2
phase. At high pressure this phase becomes, however unstable and is tranformed into more
dense polymorph, stishevite.
4.3.3.3. Sheelite and zircon structures. As follows from eq. (4.3.36), the distribution of
interstitial atoms, n[-)(p, R), results in the homogenous intracrystalline field over host lattice
sites. In this case O atoms can occupy all host lattice sites.
Let the fcc host lattice sites be occupied by O atoms and "permitted" tetrahedral interstices
of the primary Cu20-type superstructure described by eq. (4.2.10) be completely filled with
M' and M" atoms. The stoichiometric formula of such a compound is
O [(M', M")l/4 [] 3/4][(M', M")l/4 [] 3/4]
(in the case of the pyrochlore structure, "permitted" interstices of the primary structure are
filled with O atoms and their vacancies []). The ordering of interstitial atoms M' and M"
within each tetrahedral sublattice is then determined by eq. (4.3.31b):
n(M',p, R) = n~a-)(p, R) (4.3.46a)
The distribution function for M" atoms is
ns(M", 1, R) = ns(M', 2, R)
ns(M", 2, R) = ns(M', 1, R). (4.3.46b)
Placing M' atoms in tetrahedral interstices {p,R} where ns(M',p,R)= 1, M" atoms in
interstices where na(M", p, R) = 1, and O atoms in fcc host lattice site we obtain the structure
shown in Fig. 27.
The stoichiometric formula of oxides described by eq. (4.3.46) is
O[(M~/2Ml'/2)l/4 [] 3/4][(M~/2M'l'/2)1/4 [] 3/4] = M~/4M'I'/40 or M'M"O4. (4.3.47)
The antisymmetric eigenvector (4.3.44) results in a situation in which the superstructure
symmetry is tetragonal rather than cubic as in the case of the pyrochlore structure. The
structure M'M"O4 in Fig. 27 has been observed for CaWO4 (sheelite) (31)and ZrSiO4 (zircon). (3t)
4.4. Interaction of Interstitial Atoms Occupying Octahedral Interstices of the fcc

Host Lattice
As was mentioned in the beginning of this Chapter, octahedral interstices in the fcc host
lattice also form the fcc lattice which is displaced with respect to the host lattice by the vector
h0 = ½(al + a2 + a3). (4.4.1)
The ordered distribution of interstitial atoms over fcc octahedral sublattice generates an
intracrystalline field T (R) along host lattice sites as in the case of ordering over the
tetrahedral sublattices considered above. If the field is heterogeneous and amplitude of its
variation along the host lattice is commensurable with the host atom sublimation energy, host
atom vacancies at the intracrystalline field maxima must be formed. Vacancy formation may
be followed by their combined ordering with interstitial atoms, the former being ordered
along fcc host lattice sites and the latter along octahedral interstices. The theoretical analysis
of this process will be carried out below.
A simpler case is, however, possible when no structural vacancies are formed. Interstitial
l-- _l
-1
foo~J
1.,/
S
/'T I
ft~oi
i v
J
O- Si
@-0
FIG. 27. The sheelite-type secondary superstructure. O-atoms form the fcc host lattice; M and
M' metal are distributed in tetrahedral interstices in accordance with distribution (4.3.46)
(CaWO 4, ZrSiO4).
atom ordering then occurs only within the partially filled sublattice of octahedral interstices.
This may take place either if the field ~P(R), by virtue of the high symmetry of the ordered
distribution of interstitial atoms, is homogeneous and thus does not result in host atom
vacancy instability of the host lattice or if the typical interaction energies between host atoms
and interstitials are considerably less than the sublimation energy. In the latter case the
modulation of the intracrystalline field over the host lattice may be compensated by relaxation
processes such as host atom displacements and changes of electron states of atoms. This
usually occurs in compounds with metallic conductivity.
The interaction o f structural vacancies in the fcc host lattice and interstitial atoms in the
octahedral interstices can be described by the matrix Wpq(R-R ') where p, q = 1, 2. The index
1 refers to a host atom vacancy, the index 2 to an interstitial atom in the octahedral interstice.
In this notation WI~(R-R') is the interaction energy of two host lattice vacancies situated
at sites R and R'; W22(R-R' ), the interaction energy of two interstitial atoms in the
octahedral interstices R + h0 = R + ½(al + a2 at- a3) and R ' + ho; Wi2(R-R'), the interaction
energy of a host lattice vacancy at R and an interstitial atom in the octahedral interstice at
R ' + ho = R ' + ½(al + a2 + a3). The characteristic matrix then is determined by the equation
Vpq(k ) = E Wpq(R ) e -t2nkR = ~ VII(k) Vl2(k)'~ (4.42)

R \v,2(k)* v2~(k))"
Since the binding energy of the interstitial-type compounds under consideration is mainly
caused by interaction between host atoms and interstitial atoms which usually have opposite
charges, the typical interaction energy between an interstitial atom and host atom results in
attraction and thus is a negative value. To determine the interaction energy between
interstitial atom and the host atom vacancy, we should merely change the sign of the
interstitial atom-host atom interaction energy; in other words, the interstitial atom-host atom
vacancy interaction is a positive value. Following this logic, the nearest-neighbor interaction
energy, W0, between an interstitial atom and host atom vacancy is a positive value, W0 > 0.
All other nearest-neighbor interactions, vacancy-vacancy interaction W~ in the host lattice,
and the interstitial-interstitial interaction W2 in the octahedral interstice sublattice are also
positive values. Thus we have
I4/0>0 W~>0 and W2>0. (4.4.3)
The elements of the matrix (4.4.2) in the nearest-neighbor interaction model have the
following form
Vii (k) = 4 Wl[cos zrkx cos rrky+ cos nkx cos nk2 + cos rrky COS ~kz]
V22(k ) = 4 W2[cos nkx cos nky + cos 7rkxcos rrk~ + cos nky cos rtk~]
Vt2(k ) = 2 W0[cos rckx + cos nky + cos nk,] e in(kx+ky +kz). (4.4.4)
It should be emphasized that subdivision of all possible atomic positions in the fcc lattice into
the host lattice itself and octahedral interstice sublattice is quite arbitrary. Such subdivision
is natural and unambiguous if all host lattice sites are occupied by atoms whereas octahedral
interstices are occupied only partially. In the case under consideration, when vacancies are
in both, fcc host lattice and octahedral fcc sublattice, the definition of these two fcc lattices
becomes ambiguous: either of these may be named the host lattice or octahedral sublattice.
To avoid this ambiguity, we shall below refer to those fcc sublattices which have fewer vacant
sites as the host lattice. For this system the following statement is true:
the distribution function of structural vacancies along the host lattice, n(1, R) and the
distribution function if interstitial atoms along the octahedral interstice sublattice, n(2, R),
must be of the same symmetry.
Otherwise, if the function n(1, R) and n(2, R) have a different symmetry, any interaction
between host atom vacancies and interstitial atoms will make their symmetry the same---the
interaction will reduce the symmetry of the higher symmetry distribution function to that of
the lower symmetry distribution function.
The equations for n(1, R) and n(2, R) represented as the Fourier series (1.1.1) have the
same form:
n(1, R) = ~ a(l, kj) exp(i2rtkjR)
J
n(2, R) = ~ a(2, kj) exp(i27tkjR) (4.4.5)

J
where the subscript j enumerates the wave vectors entering the distribution function n (p, R);
a(1, 0) = c~, a(2, 0) = c2, Cl and c2 are fractions of sites of the fcc host lattice and octahedral
sublattice filled with host vacancies and interstitial atoms, respectively. The statement that
the functions n(1, R) and n(2, R) have the same symmetry does not mean yet that these
functions are equal. They may be "anti-isomorphic" to each other and thus be related by
equation
n(2, R) = 1 - n(1, R).
It then follows from (4.4.5) that at kj # 0
a(2, kj) = - a ( 1 , kj). (4.4.6)
J.P.M.S. 29/I-2--H
Secondly, the functions n(1, R) and n(2, R) having the same symmetry may be equal but
displaced with respect to each other by a fcc lattice translation T (phase shift) not equal to
any period of the functions n(1, R) and n(2, R), i.e.
n(2, R) = n(1, R + T).
Then it follows from eqs (4.4.5) that
a(2, kj) = a (1, kj) exp(i27~kj T), (4.4.7)
Finally, the functions n(1, R) and n(2, R) may be simultaneously "anti-isomorphic" and
shifted by a fcc lattice translation T, i.e.
n(2, R) = 1 - n ( 1 , R + T).
In this case eqs (4.4.5) at kj # 0 yield
a(2, kj) = - a ( 1 , kj) exp(i2nkj T). (4.4.8)
Equations (4.4.6)-(4.4.8) show the general relation between the Fourier coefficients, a(1, kj)
and a(2, kj), to be*
a(2, kj) = ___a(1, kj) exp(i27~kj T). (4.4.9)
Substituting (1.1.1) into eq. (2.1.1) yields a concentration wave representation of the
interaction energy:
E --UE ~j Vpq(kj)a(p, kj)*a(q, kj)

~" 2 p,q (4.4.10a)
or
N
E = -~ ~ [V,,(kj) la(1, kj)12 + V22(kj) la(2, kj) l 2
+ V21(kj)a(1, kj)a(2, kj)* + Vu(kj)a(1, kj)*a(2, kj)). (4.4.10b)

Excluding a(2, kj) from (4.4.10b) by means of eq. (4.4.9) and using (4.4.4), we may rewrite
eq. (4.4.10b) as
E~,±) = (N/2) ~ 2~±)(kj, T) [ a(1, kj) l 2 (4.4.11)
J
where
2<±)(k, T) = 4(WL + W2)[cos rckxcos 7~ky+ cos 7tkxcos 7~k~+ cos rckycos 7~k~]
___4 W0[cos 7tkx + cos 7~ky+ cos nkz] cos 7r(kx + ky + kz - 2kT) (4.4.12)
4.5. Primary Interstitial Superstructures with Fixed Stoichiometry Formed by

Ordering of Interstitial Atoms over Octahedral Interstices of the fcc Host Lattice
Equation (4.4.12) shows that the analysis of two sublattice systems is, in fact, reduced to
that of a simple single-sublattice system. The sole insignificant complication is that the
*Strictly speaking, this conclusion is valid in the relevant case when the distribution functions, n(p, R) also meet
the maximal amplitude principle, i.e. one of the amplitudes in (4.4.6) (amplitude of the dominant wave) is much
larger than all others.
function 2(±)(k, T) proves to be dependent not only on the wave vector k, but on the
additional discrete indices which are the translation vector T situated within the super-
structure unit cell and signs (_+). The indices enumerate branches of the function 2 (±)(k, T)
within the first Brillouin zone.
Reasoning similar to that of Section 4.2 results in the list of suitable stars (4.2.1) and (4.2.2)
which provide the complete fulfilment of the maximal amplitude principle. Substituting the
wave vectors k0 from (4.2.1) and (4.2.2) into (4.4.12) and selecting at each wave vector k0 the
signs ( + ) or ( - ) and the translation T so that the function 2(+)(k, T) would assume the
minimum value, we obtain the spectrum of numbers. The lowest value, min 2(-+)(k, T), is
determined by comparing these numbers. Fig. 28 demonstrates the dependences of the
minimal values of 2(±)(k0, T) at k0 taken from the list (4.2.1) and (4.2.2) on the parameter
(1411 + Wz)/Wo. The figure shows that
(i) at (W~ + WE)/W0 < ½ the minimum of 2(±)(k0, T) falls on k0 = (000)
(ii) at (W~ + Wz)/W0 > ½the minimum of 2(+)(k0, T) falls on k0 = { 100} at T = 0 for
the branch ( + ).
(i) The case of (W1 + Wz)/Wo < ½.
This simplest case corresponds to the disordered distribution of vacancies along the fee host
lattice and interstitial atoms along the fcc octahedral site sublattice. Such a distribution yields
the NaCl-structure symmetry,
(ii) The case of ( W 1 --]- W2) / W 0 > 1.
In this case the minimum of 2(~:)(k0, T) is provided by T = 0, k0 = {100}, and the
branch (+).
We will not consider the nonphysical cases of the superloose structures where vacancies
occupy more than a half of the host lattice sites. Such loosely packed structure can hardly
exist. Besides, by the definition given above, the host lattice is chosen so that it contains fewer
vacancies than the octahedral interstice sublattice.
Therefore we will consider below the distribution function of host lattice vacancies, n (1, R ),
for which el ~<½. The star {100} providing the minimum of 2(±)(k0, T) generates two
distributions, n(1, R), whose values are either unity or zero on all fcc lattice sites {R}:
n~(1, R) = ½+ ½exp(i2nk'o"R) = ½+ ½exp(i2nz) (4.5.1)
and
lr,~a~t6R-L
n2(1, R) = ¼ q- 4tv _ ,~a~t6R
~ + ea~kS"R]= ~~ + ~[e
1 anx + e,2ny + e,2~] (4.5.2)
where
k~ = (100), k~' = (OLO), k~" = (OOl).
For the distribution (4.5.1)
a (I, k~') : 1.
Since the minimum of 2<±)(ko, T) occurs at the branch ( + ) and T = 0, eq. (4.4.9) yields the
only nonzcro Fourier coefficient for n~(2, R) at k0 # 0. It is
a(2, k ~') = a(1, k'o") = ½. (4.5.3)
The coefficient a(2, k0" ) = ~ provides the distribution
nl (2, R ) = ½+ ½exp (i2nz). (4.5.4)
¢ K,(aaa:
2 ~=Hoo)
s
s K-/¾½1~)
.r K=(½ ~ U)
6 x-('.4f4,~)
z K:(t,~a)
g K--J~D)
9 K-/~00)
¢0 K-f~ ~ 0 , )
2
5'
~÷~
i
-I ~/ t/l
FIG. 28. The dependence of eigenvalues k(+)(k, T) on the parameter

W~ + W2
Wo
for various k o taken from the list (4.2.1) and (4.2.2).
Therefore
~1 ½exp(i2rrz)at p
nl(p, R) = + = 1 (4.5.5)
+ ½exp(i2~zz) at p =2.
Placing vacancies at fcc lattice sites where nl(1, R ) = 1 and interstitial atoms in octahedral
interstices at R + ½(al + a2 + a3) where nl(2, R) = 1, we obtain the primary structure.
In this structure host atoms and interstitial atoms form the same quadratic net in the (001)
plane situated exactly one above the other. Such an atomic pattern seems to be unstable since
any slip of a quadratic atomic net in the (001) plane with respect to the nearest atomic net
may occur without hindrance, i.e. without atomic collisions. For example, the slip of every
other (001) plane by the distance ½al followed by homogeneous contraction of the entire lattice
along the [001] axis by the value x/~ results in a radical fcc lattice rearrangement and
formation of a more closely packed CsC1 structure. Therefore, the structure of (4.5.5) is
unstable with respect to host lattice rearrangement and thus cannot be observed. This
conclusion is in agreement with the structure study results.
Let us construct the structure generated by the distribution (4.5.2). It follows from (4.5.2)
that
a(1, k~) = a(1, k"o) = a(1, k~') = ¼ (4.5.6)
For the branch ( + ) at T = 0 which provides the minimum of 2~-+)(k0, T), eq. (4.4.9) yields
/
a(1, k~) = a(2, k0) = ¼
a(I, k[') = a(2, kg) = ¼
lit lit l
a(1, k 0 ) = a(2, k 0) =
and we have a distribution for interstitial atoms, n2(2, R), equal to the distribution (4.5.2) for
host lattice vacancies, i.e.
n2(1, R ) = n2(2, R) _- gl + g[e
i , 2 n x + e~.y + e,2=] (4.5.7).
Placing vacancies in fcc host lattice sites {R} = {x, y, z} where n2(1, R) = 1 and interstitial
atoms in octahedral interstices {R +½(a~ +a2+a3)} where n2(2, R ) = 1, we obtain the
structure of Fig. 29. If fec host lattice sites are occupied by O atoms and octahedral interstices
by metal atoms, the stoichiometric formula of the oxide described by eq. (4.5.7) is
([x/403/4)(MI/4[-13/4)=M1/403/4 or MO 3 (4.5.8)
where the formula [1/4 03/4 in the first parenthesis describes the relation between the vacancies
and O atoms in the host lattice, whereas the terms M1/4I--13/4in the second parenthesis describes
the relationship between interstitial atoms M and their vacancies [] in the octahedral
interstices; [ refers to a host atom vacancy, [] to an interstitial atom vacancy. The MO3
oxide may be formed for six-valent metals and is observed in ReO3.°9)
Equation (4.5.8) also describes the isomorphic compound in which anion vacancies, []k-l,are
substituted by second type metal atom, M'. Since such a structure is more closely packed than
the ReO3 structure, it is supposed to be more stable. Its stoichiometric formula can be
obtained from (4.5.8) by substituting M' for Ik-]:
(M~I40314)(MlI4[-]3/4)-~M~/4M1/403/4 or M'MO 3 (4.5.9)
The resultant structure is the widespread perovskite-structure (Fig. 30). The classic example
of this structure is perovskite, CaTiO3, [(Cat/403/4)(Til/4[]3/4)(19)].
4.6. Secondary Superstructures Formed by Combined Ordering of Interstitial Atoms

in Octahedral Interstices and of Vacancies in the fcc Host Lattice
As was shown in Section 4.5, the maximal amplitude principle results in two primary
superstructures with the fixed stoichiometry. One of them is described by eq. (4.5.5), the other,
by eq. (4.5.7). The former structure contains too many vacancies to be stable and undergoes
the host lattice rearrangement yielding a closely packed structure. However, it should be
stressed that the deviation of the structure from its equiatomic composition might result in
stabilization of the structure. There is only one way for such a deviation to occur, the
reduction of the number of vacancies in the host lattice by introducing excessive host atoms.
The structure stabilization occurs because of "blocking" of displacements of (001) planes
along the [100] direction. Such displacements would result in collisions of interstitial atoms
eeo,
FIG. 29. The ReO3-type superstructure formed due
to simultaneous ordering of oxygen vacancies in the
fcc host lattice and interstitial M-atoms in octa-
hedral interstices in accordance with the distribution FIG. 30. The perovskite structure (CaTiO3). O , Ca;
(4.5.7). O, Re; O, O. O, Ti; ©, O.
with additionally introduced host atoms. In this situation, when the host lattice remains
stable, secondary ordering may take place. After removal of a certain amount of interstitial
atoms, an octahedral sublattice may also be involved in the secondary ordering. The
secondary ordering then occurs within two "permitted" sublattices. The first "permitted"
sublattice (p = 1) is formed by vacant sites of the host lattice of the primary superstructure
(4.5.5) where nl°(1, R) = 0. Vacant sites of this sublattice are occupied by excess host atoms.
The second sublattice (p = 2) is formed by octahedral interstices permitted for interstitial
atom occupancy in the same primary superstructure. These "permitted" interstices where
n°(2, R) is described by eq. (4.5.5)] are occupied by interstitial atoms involved in the
secondary ordering.
In secondary ordering, we should consider only interaction energies Wpq (r -- r") of excess
host atoms at "permitted" host lattice sites {1, r} and interstitial atoms at "permitted"
octahedral interstices {2, r }.
According to the theoretical concept formulated in Section 2.8, the energy change caused
by the secondary ordering is determined by the characteristic matrix
Vpq(k ) = ~ Wpq(r) exp(-- i2rckr) (4.6.1)

r
where the summation is carried out over the reference vector, r, labeling the "permitted" sites
{p, r} of both sublattices. Equation (4.6.1) holds if the reference vectors {r} form a Bravais
lattice. This is exactly the case of the primary superstructure described by eq. (4.5.5).
As before, we may extend the summation in eq. (4.6.1) to all fcc lattice sites introducing
the "weight factor" n°(p, R) which, by the definition of the primary superstructure, is equal
to unity at "permitted" sites and to zero at "forbidden" sites:
Vpq(k) = ~ W~(R)n°(p, R) exp(-i2nkR). (4.6.2)

R
Substitution eq. (4.4.5) into (4.6.2) yields
Vpq(k ) = ~ Vpq(k - koj)a°(p, koj) (4.6.3)

J
where the Fourier coefficients a ° (p, koj) are referred to the primary superstructure distribution
function (4.5.5). In compliance with eq. (4.5.5) all Fourier coefficients a°(p,k) except
a°(p, 0) = a°(p, k~") = ~ at p = 1 and p = 2 vanish.
Using this in eq. (4.6.3) we have
~pq(k) = ~Vpq(k) + ½Vpq(k - k~"). (4.6.4)
Substituting the matrix elements (4.4.4) into (4.6.4), we have
Vii(k) = 4W1 cos r~kxcos nky
V22(k) = 4W2 cos nkx cos nky
V12(k) = 2W 0 cos rckzexp(in(k x + ky + kz)). (4.6.5)
Since it is more convenient in this case to consider the interaction of host atoms and
interstitials rather than host atom vacancies and interstitials, as done above, we must change
the sign of W0 in eq. (4.6.5). This gives
Vii(k) = 41411cos rckxcos ~zky
V22(k) = 4W2 cos nk, cos nky
V12(k) = - 2W0 cos nk~ exp(i~t (kx + ky + k~)) (4.6.6)
where W I > 0 , W2>0, W0>0.
Substituting eq. (4.6.6) into the equation
E = N ~ ~(k)?z(p, k)*?~(q, k) (4.6.7)

2 p.q
for the interaction energy [it is the counterpart of eq. (4.4.10a)] and taking into account the
relation
a(2, k) = +__a(1, k)exp(i2~kt) (4.6.8)
similar to eq. (4.4.9) where t is a translation of the primary superstructure, a (p, k) amplitudes
of the secondary superstructure, we have
E~+) = N ~ ~[<±)(k:, t) I~(1, kj)12 (4.6.9)

2j
where
~ ) ( k , t ) = 4 ( W 1 + W2) cos nk~cosnkyT-2WoCOSnk~cosn(k~+ky+k~-2kt) (4.6.10)

The absolute minimum of the function (4.6.10) is attained for the "branch" ( + ) at
= ' "
t = rE½½01 + a2) and falls on k = k0 and k = k 0. Then
min ~[~±)(k, t) = ~[<+)(k~, tt½½01)= 2~+)(kg, tt½½01) = - 4 ( W l + WE) -- 2W0 (4.6.1 1)
The occurrence of complementary dominant waves
a(p, k ") ea~k~' and a(p, k'o')e'2~k~"

of the secondary superstructure corresponding to k~ = (100) and k~ = (010) results in
formation of the superstructure (4.5.7) considered above.
4.6.1. Homologous phases M , 03,_ l

Refinement of the interatomic interaction model by including weak long-range interaction
may in certain cases lead to a small s h i f t , of the minimum of ~[~)(k, t) from the point
k~ = k~ = (100) (4.6.12)
As shown in Section 3.4, in this case the series of homologous phases occurs.
4.6.1.1. Stoichiometric formula. Let us first determine the stoichiometric formula of a

homologous phase. Both "permitted" sublattices in a homologous phase must have the same
fraction of occupied planes equal to either
n n
cst = 2n - 1 or cst = 2n + 1
The reason for that is readily seen. Indeed, repeating the same arguments which brought us
to eq. (3.3.28) and (3.3.29b), we obtain
n
~1 = c s t H r = ~ Mr
2n -- 1
1
- 2(2n - 1) Hr (4.6.13a)
or
n
k ! = Cstl-Ir = ~ tt r
2n+l
1
= 2(2n + 1) Hr (4.6.13b)
where
Mr = 2 k r .Jr_H s (4.6.14)
H is a reciprocal lattice of the primary superstructure [H = H<00~)+ 2Hf=, where Hfo: is an
arbitrary reciprocal lattice vector of the fcc crystal]. Equations (4.6.13) show that the wave
vector k~ of the dominant concentration wave unambiguously related to the fraction of
occupied planes equal to either
n n
or
2n - 1 2n + 1"
Since the wave vector of the dominant wave is evidently the same for both sublattices, the
fraction of occupied planes in both sublattices must also be the same.
This statement immediately brings us to the important conclusion that the atomic
distributions, n (1, r) and n (2, r) meeting the maximal amplitude principle should be described
by the same distribution function which may, however, be shifted with respect to each other
by a primary superstructure translation t:
n(2, r) -~ n(1, r + t). (4.6.15)
This means that
a(2, k~ ) = a (1, k~ ) exp(i2nk~ t) (4.6.1 6)
Let us assume that the fraction of occupied planes of both "permitted" sublattices is
n
cl = c2 = cst = 2n - 1
for this fraction is greater than

n
cst- 2n + 1
and thus provides a more closely packed structure.

Therefore in the desired secondary superstructure:
(i) excessive host atoms, O, occupy the fraction
n
cst = 2n - 1
of the "permitted" host lattice sites, i.e. the fraction n / ( 2 n - 1) of host lattice
vacancies, [], in the stoichiometric primary superstructure;
(ii) interstitial atoms, M, occupy the fraction
n
Cst - -
2n - 1
of the "permitted" octahedral interstices which are completely filled with M atoms
in the stoichiometric primary superstructure.
In this light we should perform the substitutions
(0.~:~ ~ql- "~)2._, for [] (4.6.17a)
and
( M ~ I - 1 , _ ~_~) for M (4.6.17b)
in the stoichiometric formula

(O½[]½) (M½[]½) (4.6.18)
of the primary superstructure described by eq. (4.5.5). The substitution (4.6.17) in (4.6.18)
yields
(0½(Oj []1_ . , ) ½ ) ( ( M2.-,

~ . D r _ 2.-,
.~)½[]½)
=(03n-1 [ ] n-, ) M n [ ] 3.-,
= 0 3.-, M . (4.6.19)
2(2n- l) 2(2n- 1)
or
Mn 03n_ 1 (4.6.20)
4.6.1.2. The generating plane. It follows from eq. (4.6.13a) that the generating plane which
produces the structure of a layer homologous phase is determined by the reciprocal lattice
vector Hr. To find Hr, we should investigate the spectrum 2~±)(k, t).
It follows from (4.6.10) that the only branch, (+), must be considered. Substituting
k~ = k , + ~ into (4.6.10) results in
~ ( + ) ( k r -1- lr, t ) ~- - 4 ( W 1 + W2) cos 7cz x cos/z'cy
+ 4Wocos nrzcos n(zx + Zy+ Zz- 2~t - 2krt ). (4.6.21)

Using (4.6.13a) for z in eq. (4.6.21), we obtain the series:
~(+) (kr + 2(2n1_ 1) H~, t ) = -4(W~ + W2) cos 7["2(2nH r x-- 1) COSn 2(2nHry
-- 1)
+4W0cos
7t2 ( 2Hr~
n-
1)cos rc (Hr~+Hry+n~2Hrt
2(2n- -2k~t ) . (4.6.22)
Arranging the vectors H, meeting the definition (4.6.14) in an increasing order of
(\kr -~ ' ,,r,,)

2(2n - I)
we obtain the series
Hr= (200) at t = tf½½ol,Hr= (240) at t = tt½½01. . . . (4.6.23)
The series (4.6.23) implies that the first reciprocal lattice vector H, = (200) provides the
minimal value of
'~+) (kr + 2(2n 1- 1 ) H , t )
at t =tt½½0l, etc. The vectors H~= (200) and H~= (240) then are the most probable
"candidates" to be chosen. The final decision in favor of one of these two reciprocal lattice
vectors cannot be made unless the model incorporates long-range interaction.
The wave vectors of the dominant concentration wave in the case of H, = (200) are
determined by eq. (4.6.13a),
n
kI - (200), (4.6.24)
2n - 1
and the wave vectors
n
k ~ - 2n - 1 (240) (4.6.25)
in the case of Hr = (240).

Consequently, the motif of the layer homologous phase MnO3n_ l consists of s I = 2n - 1
planes (200) or (240).
4.6.1.3. The sequence of alternating planes. The sequence of occupied and vacant planes in
the layer homologous phase is also determined from the maximal amplitude principle by the
clock diagram (see Fig. 1). For example, at n = 9, we have the homolog M9026 with the
superstructure period, s~, determined by eq. (2.5.22):
s1 = 2 n - 1 = 2 . 9 - 1 = 17
The sequence of occupied and vacant planes drawn in the "permitted" sublattices may be
taken from the clock diagram (see Fig. 1). It is
t~ O O [] O [] O ~ O [] O [] O rk-10 [] O [] O O
[] M M [] M [] M [] M [] M [] M [] M [] M [] M M (4.6.26)
The shift between two sequences shown in (4.6.26) by the arrow is equal to
t[½½01+ ho = ~(alt + a2 ) + ~(alz + a2 + a3 ) = al + a2 + ~a
31
The corresponding structure is drawn in Fig. 31.
4.6.1.4. Observation results. The structures of the homologous series MnO3n_1 predicted in
Section 4.6.1. were indeed observed.
The structure V205 being a member of the series M, O3,_ t at n = 2 is generated by the plane
(200), and has the predicted sequence of occupied and vacant (200) planes in "permitted"
sublattices.(52)
The homologous series of oxides (Mo, W),O3,_1 with 8 ~<n ~ 14 was also found. (~6) In
complete agreement with the theory, the atomic distribution in these phases is generated by
the dominant wave with wave vectors
n
kl -- 2 n ~ (240),
the entire layer structure being generated by alternation of (240) planes. The sequence of
occupied and vacant (240) planes in the "permitted" host lattice and octahedral sublattice
is similar to that derived for the structure M9026[see (4.6.26)]. As shown in Section 2.5, this
sequence provides the maximal possible amplitude of the dominant wave with
n
kl = 2n - 1 H(24o).
t,-
'a¢~c
O-Mo
O-0
FIG. 31. The structural motifcorrespondingto M09026 long-periodlayersuperstructurebelongingto
the homologousseries M,O3,_i.
It is noteworthy that the same sequence occurs in the absolutely different homologous series
Ti, O2n_l based on the bcc host lattice [see Section 3.4]. The latter m a y serve as convincing
evidence that the proposed mechanism based on the maximal amplitude principle gives a
correct understanding of the nature of the homologous phases. F o r illustration, let us
consider the oxide Mo9026 belonging to the M, O3,_~ series. Fig. 32 (a) and (b) displays two
plots; (a) the predicted dependence of squared moduli of the concentration wave amplitudes
related to the superlattice wave vectors k s = skl(s = 1, 2 . . . . . 17) entering the distribution
function n(p, R ) for Mo9026. These squared moduli are calculated from eqs (2.5.17):
n 9
sin 2 rrc~s sin 2 7 z ~ - ~ s sin 2rc - ~ s
s 2 sin 2-~ s (2n - 1)2 sin 2 n___~s 172 sin 2 rrs

sl 2n -- 1 17
Figure 32(b) plot shows the measured powder diffraction line intensities at the corresponding
superlattice vectors of Mo9026. These two plots qualitatively coincide. The maxima of both
plots fall on the superlattice vector kl = 9(240) related to the dominant wave. Intensity of
reflections with even s are negligibly small, whereas intensities of odd s reflections drop with
increase o f the reflection number s. A better agreement of calculated and observed diffraction
patterns m a y be attained if atomic displacements caused by ordering are taken into account.
4.7. Spinel as a Superstructure Based on Occupation o f Octahedral and Tetrahedral

Interstices o f the f c c Host Lattice
The situation is more complicated when interstitial metal atoms occupy both octahedral
and tetrahedral interstices: for example, M ' atoms occupy tetrahedral and M" atoms
(a)
(b)
¢ 2 ,3 # 5" 6 7 8 ,5'
¢6 ¢$ f~ ¢8 /2 H fO 9
FIG. 32. Intensities of superlattice reflections in the diffraction pattern of the MO9026.(a) Intensities
calculated in accordance with (2.5.17). (b) Observed intensities.
octahedral interstices. Since octahedral and tetrahedral sites of the fcc lattice are crystal-
lographically nonequivalent, the theoretical analysis can hardly be as easily performed as
before. Nevertheless, one widespread particular case, the spinel structure, is worthy of
detailed consideration. To do it, we will discuss superstructures formed by interstitial metal
atoms filling tetrahedral and octahedral interstices of the fcc host lattice composed of oxygen
atoms.
In this case it is more convenient to utilize different notation i.e. to choose as a reference
lattice the fcc sublattice of octahedral sites rather than the fcc host lattice, as was done in
the previous sections. Then octahedral sites are designated by the vector {R}, T1 and T2
tetrahedral sites by the vectors {R + ¼(al + a2 + a3)} and {R - l(a I + a 2 -']- a3)}, respectively,
and fcc host lattice sites by the vectors {R +½(al + a2 + a3)}.
Let the interaction energy of an M' atom in a tetrahedral interstice and a M" atom in the
octahedral interstice separated from the M' atom by the shortest distance,
/-T_
r 0 = - ~ a,
be W0. As in Section 4.1, the nonzero interaction energies of M ' - M ' atomic pairs in
tetrahedral sites separated by distances,
1 a a~_
F1 ~ 5a,/'2 ~ ~ ~ /'3 ~ , /'4 ~ a~
are equal to W1, I'I12, W3 and I4/4, respectively. The constants W1, I4/2, W3 and W4 thus
characterize the interatomic interaction within the tetrahedral sublattices, whereas the
constant W0 characterizes the interaction between atoms in the tetrahedral and octahedral
sublattices, i.e. is a coupling parameter between these two types of the sublattices.
One may readily see that the interaction energy, I4/0 of the nearest M'-M" pair is mainly
determined by the contact repulsion caused by overlap of the electron shells of the nearest
M' and M" atoms. It occurs since the separation distance,
x/~a
r°- 4 '
is usually considerably smaller than the half sum of the atomic diameters of the atoms making
the pair. In this situation the repulsive interaction energy W0 proves to be much higher than
all other interaction energies. Therefore we may rewrite the inequalities (4.1.2) as
w0>> w, > W2> w3> W,>0. (4.7.1)
Since the contact repulsion W0 far exceeds all other interactions, any superstructure
containing the nearest M'-M" atomic pairs must be unstable. These pairs would make an
unduly large positive contribution into the interaction energy. In other words, we can
conclude that no stable superstructure should contain the nearest M'-M" atomic pairs and
therefore the total interaction energy should not depend on W0.
The latter means that without loss of generality in a stable superstructure we may put
W0 = 0. Indeed, any value of W0 including W0 = 0 does not contribute into the interaction
energy of a superstructure without the nearest M'-M" pairs. On the other hand, assuming
the coupling parameter W0 between the octahedral and tetrahedral sublattices to be equal to
zero, we come to the conclusion that the ordering within the octahedral and tetrahedral
sublattices must occur independently; to put it differently the ordering in tetrahedral
interstices can be considered ignoring the presence of M" atoms in octahedral interstices and
vice versa.
The ordering in tetrahedral interstices of the fcc host lattice has been considered in Section
4.3.3. As was shown in Section 4.3.3, the atomic distribution of M' atoms in tetrahedral
interstices is described by eq. (4.3.31),
nM,(1,R)=nM,(2, R)
= ~ +( e 1l i2~tx-Jt-ei2ny "1- e ~2nz) -+- l(ein(x+Y+Z) -'1- e in(-x+y+z) -k- e in(x+y-z) + e in(x-y+z) )
at
4 W4
5x/~ < W33< 1. (4.7.2)
The atomic distribution of M' atoms in tetrahedral sites being known, we may make the
next step, viz. find those octahedral sites in which M" atoms can be placed without formation
of the nearest-neighbor M ' - M " pairs. For this purpose we should find the intracrystalline
field, 7'(R), on octahedral sites produced by the distribution (4.7.2) of M' atoms in the T~
and T2 tetrahedral interstices. The octahedral sites where ~U(R)= 0 are exactly these sites.
Indeed, the octahedral sites where ~ ( R ) = 0 do not have the nearest M' atoms because
otherwise M" atoms placed in such octahedral sites would produce the nearest-neghbour
M ' - M " pairs resulting in a nonzero contribution W0 into the intracrystalline field 7J(R).
The distributions (4.7.2) in the T~ sublattice (p = 1) and T2 sublattice (p = 2) generate the
field (4.3.34).* Substituting k = 0 into (4.1.16) yields
W1 (0) = W 2(0) = 4 Wo (4.7.3)
Since in eq. (4.7.2)
a(1, 0) = a(2, 0) = a(1, kj) = a(2, kj) = 1
where kj are vectors of the star {½½½}, and
ff'p(k)=0 at k={100},
we may rewrite eq. (4.3.34) as follows
~trJ(+)(R) ----- W0 -Jr-½W 0 [ - - e in(x+y+z) + e in(-x+y+z) --I- e in(x-y+z) + e i~<x+y-z)] (4.7.4)
Substituting the coordinates of the fcc lattice sites {R} = {x,y, z} into (4.7.4), one may see
that the intracrystalline field ~ ( R ) can assume only two values on fcc lattice octahedral sites,
either 0 or 2 W0. The octahedral sites where q~(R) defined by eq. (4.7.4) vanishes are described
by the function
noct= ½ _ t [ _ ein(x+y+z) + ein(-x+y+z) + ein(x-y+z) + ein(x+y-z)] (4.7.5)
This function takes on the value 1 at the octahedral sites where 7J(R)= 0 and zero at the
sites where ~ ( R ) = 2W0. Placing M" atoms in the octahedral sites where noct ( R ) = 1 we
obtain a superstructure without the nearest-neighbor M ' - M " pairs. In this structure the
function no,(R) describes the distribution of M" atoms along the fee octahedral sublattice.
The fcc-based superstructure where O atoms occupy fcc host lattice sites; M' atoms
*Recall that the choice of the octahedral sublattice here as the reference lattice leads to the conclusion that the
foe octahedral sublattice in this section plays the part of the fcc host lattice in Section 4.3.
T , .LT I J,
(b) (c)
FIG. 33. The fcc-based superstructure M'M~O4 corresponding to the spinel structure. Fcc host lattice
consists of O atoms. M' atoms distributed in tetrahedral interstices according to eq. (4.7.2); M" atoms
are distributed in octahedral interstices in accordance with eq. (4.7.5). (a) Schematic drawing of the
spinel unit cell composed of 8 host lattice face-centered cubes of two different types, (b) and (c) show
these two face centered cubes composed of O atoms which are filled with interstitial M' and M"
atoms in different manner. @, O; O, M'; O, M".
tetrahedral sites where nM,(p,R ) = 1; and M" atoms octahedral sites where no~t(R)= 1 is
shown in Fig. 33. One may easily see that this is exactly the spinel structure) 31)
According to eqs (4.7.2) and (4.7.5), the stoichiometric formula of the spinel structure is
(M'I'/2 [ ] 1/2) [M~/8 [~]7/8] [M~/8[]7/8 ] O = M'l'/2 M~/40 (4.7.6)
or
M'M~O4
The spinel structure is certainly stable if the interaction between M" atoms in octahedral
interstices is ignored. The situation becomes more complicated if the M"-M" interaction is
not ignored. Then we have two cases:
(i) the total interaction energy of M" atoms assumes its minimum value for the
distribution (4.7.5)
(ii) the total interaction energy of M" atoms is minimized for the distribution other than
(4.7.5).
In the case (i), the spinel structure is surely stable. As for the case (ii), this is uncertain.
Therefore, the relations between interaction energies of M"-M" atomic pairs providing the
stability of the ordered distribution (4.7.5) is the sufficient condition for the stability of the
spinel structure.
4.7.1. The interaction energy of atoms occupying octahedral interstices

The pairwise interaction energy of M" atoms arbitrarily distributed over octahedral sites
is
Eo~t = 1 ~. Wo~t(R _ R,)no,(R)noct(R, ) (4.7.7)

2 RR"
where Woct(R-R') is an interaction energy of two M" atoms situated in octahedral

interstices at R and R', respectively; the summation is performed over all fcc lattice sites.
The concentration wave representation of the interaction energy (4.7.7) is
I
Eoct = ~ N ~ Vo~t(k)]ao~t(k)12 (4.7.8)
k
where aoct(k ) are amplitudes of concentration waves generating the distribution
noct(R) = ~ acct(k) exp(i2nkR), (4.7.9)

k
Volt(k) = ~ Woct(R) e x p ( - iZzckR). (4.7.10)

R
Introducing the nearest- and next-to-nearest interaction energies W~ t and W~ t, for M"-M"
pairs separated by the fcc lattice translations, {~ ~ 0} and {a00}, respectively, we have the
characteristic function (4.7.10) in the form
Vo,(k) = W~t[cos nkx cos rcky + cos rckx cos nkz + cos nky cos nkz]
+ W~t[cos 2rrk x + cos 2nky + cos 2nkz]. (4.7.11)
It may readily be verified that at [,//-oct
,, 4 /rv/ l./.,roct .~ 1
2 4 the minimum of the characteristic function
I-
(4.7.11) falls on the star vectors {½½½}. Therefore, the conditions (4.7.1),
W 4 4 l'//'°c t 1
> 5~-~' and ~W2 >-4 (4.7.12)
provide the stability of the spinel structure in the framework of the short-range interaction
model.
The relations (4.7.12) demonstrate that interaction energies should not decrease too fast
with the distance to provide the stability of the spinel structure, or, which is the same, their
range should not be too short. We shall consider below the case of long-range Coulomb
interaction energies.
4.7.2. Stability of the spinel structure in the case of ionic binding
In the case of ionic binding, Coulomb interatomic interaction makes the main contribution
into the binding energy. If the spinel structure is assumed to be stable, the following question
may be posed, what charges of interstitial metal ions, M' and M", should be chosen to attain
the maximal stability of the spinel structure, i.e. what charges of ions minimize the Coulomb
interaction energy of interstitial ions? An answer would enable us to predict the valencies of
metal atoms providing the stability of the spinel structure.
The characteristic matrix for interaction of interstitial atoms placed in octahedral and
tetrahedral interstices is
/VII( / ) V12(k) V13( / )
Vpq(k)=~ Wpq(R)e-i2'tkg=[v12(k) V,l(k ) V,3(k)* ~ (4.7.13)
\v,3(k)* vl3(k) /
where the subscript p = 1 (or q = 1) enumerates interstitial sites of the T1 sublattice; p = 2
(or q = 2) enumerates interstitial sites of the T 2 sublattice, and p = 3 (or q = 3) labels
octahedral sites. The relations
V,(k) = V2z(k ) Vz3(k)= V,3(k)* (4.7.14)
utilized in the matrix (4.7.13) can be obtained by applying the crystallographic symmetry of
the fcc lattice with respect to the inversion,
R~-R, 1--.2, 2 ~ 1
in the definition (4.7.13).
In the relevant case of the Coulomb interaction, the matrix Vpq(k) may be represented as
Vpq(k) = epeqMpq(k ) (4.7.15)

a
where Mpq(k) is the dimensionless matrix depending only on the geometry of the fcc lattice,
~etetr
ep=(eo~t
if p = 1,2
if p = 3
(4.7.16)
etetr is the charge of a M' ion in the tetrahedral sublattices, eo~t the charge of a M" ion in the
octahedral sublattice. By the definition
M.q (k) V a exp( - i2~kR). (4.7.17)

I R + he - hq I
m l , (k) = M22 (k) = M33 (k). (4.7.18)
The analysis of the interaction energy enables us to determine the ratio
# - - eoct
etetr
which provides the interaction energy minimum.
The total pairwise interaction energy of M' and M" ions arbitrarily distributed over
octahedral and tetrahedral interstices is
E = 1_ ~ Wpq(R - R')n(p, R)n(q, R )

2 p.q,R,R'
or in terms of the concentration waves
E = ½N ~ Vpq(k)a(p, k)*a(q, k) (4.7.19)

P,q
J.P.M.S29/I-2-I
where
fnM,(1, R) if p = l
n(p,R)=~nM,(2, R) if p = 2
I,nM,,(3, R) if p = 3
n(p, R) = ~ a(p, kj) exp(i2rckjR). (4.7.20)

J
The distributions (4.7.2) and (4.7.5) for the spinel structure can be rewritten in the dense form:
ill/ l(l/
n(p,R)=~n(2, R) = ~ 1 + ~ I [ei2'~"TR+e'2~"~R+e'2"~R]+-~{1)ei'("~+"2+"'I)R
\n(3, R) \4/ \0/
+ [ei,(-a, +,~+o~) + ei,(,~ ,~+,~m + e~(,r +,~-a~)R]
Comparing (4.7.21) and (4.7.20), one can see that the nonzero amplitudes of the concentration
t (4.7.21)
waves
/a(1,k)\
a(p,k)=|a(2, k)~
\a(3, k)/
which generate the spinel structure are
a(p,O) = ~
(1/ (4.7.22a)
\½/
a(p, ko)= ~ at k0={100} (4.7.22b)
81 at
ko=(½½½)
a(p, ko) =
~ at ko=(~½½), (½~½),(1~9.
iT
(4.7.22c)
Utilizing (4.7.22) and the definition (4.7.15) in (4.7.19), we have
E = ½N ~ epeqipq(O)a(p, O)a(q,O)+ ½N ~ epeq E Mpq(koj)a(P,koj)a(q, koj)*

p,q p,q koj~ {100}
"[-½NZ epeq 2 Mpq(koy)d(p,koj)a(q, koj)*. (4.7.23)

p,q l 1I
The firstterm in (4.7.23) combined with the corresponding host-host and host-interstitial
atom interaction always vanishes becausc of electroneutrality of the system. That is why it
can be ignored.
The second term in (4.7.23) describes only interaction of M' ions occupying the tetrahedral
sublattices since a(3, k00o}) = 0 [see eq. (4.7.22b)]. Thus it does not depend on the charge ratio
= eoct/etetr.
The third term in (4.7.23) includes however the interaction of unlike ions and thus it
depends on charge ratio # = eoct/etetr. Therefore to determine the optimal ratio, # = #0,
providing the interaction energy minimum, it is sufficient to consider the third term of
eq. (4.7.23),
E,11!1
12225
=½N L epeq L Mpq(koj)a(p, koj)a(q, koj)* (4.7.24)
P,q k o j e {I ~1 ! }
This term is a quadratic form of the matrix
Vpq(k ) : ep eq Mpq (k ).
a
As known, a quadric form assumes its minimum value if the variables are proportional to
the components of the eigenvector related to the lowest eigenvalue of the matrix making the
quadric form. Applying this statement to the quadric form (4.7.24), one may conclude that
it assumes the minimum value when the amplitudes a(p, koj) prove to be proportional to the
components of the eigenvector O~o(p,koj) related to the minimum eigenvalue 2~0(k0j) of the
matrix
epeq gpq (koj) .

a
This reduces the minimization procedure to merely finding the optimal ratio
foot
#0 = -
etetr
providing the eigenvector v,0(p, koj) to be proportional to the amplitudes a(p, koj) given by
eq. (4.7.22c). Let us find the eigenvalues and eigenvectors of the matrix (4.7.13) at k0 = {½515}.
Any vector k0j of the star {½½½} meets the equality, k0j = - koj to within a reciprocal lattice
vector. It results in the relation
Vpq(ko) = Vpq(-ko)= Vpq(ko)*

which shows that the elements of the matrix Vpq(kO)a r e real numbers. In this case the matrix
(4.7.13) has following eigenvalues and eigenvectors at k0 = {½1155}."
~l(ko) = V . ( k o ) - I V,z(k0) I (4.7.25a)
ol (p, ko) = - ~ (1, - 1, O) (4.7.25b)
and
,~ ± ~(k0) = ½{ 1"1~(k0) + V12 (k0) + V33(k0)
___x / [ v . (ko) + v,~(ko) - v~(ko)] ~ + 8 v,~(ko) ~} (4.7.26a)
1
o¢+)(p, ko) = ~/2ct~±) + B~±)(0t(±), ct(±), /~(±)) (4.7.26b)
where
~<_+~= ~{vH (ko) + Vl2(ko) -- V~(t.o)
-T-,/[VH(ko) + V12(ko) - V33(ko)]z + 8Vl3(ko) 2} (4.7.26c)
tic_+)= 2 Vl3 (ko). (4.7.26d)
The lowest eigenvalue corresponds to the index ( - ) in eq. (4.7.26a). In compliance with eq.
(4.7.18), we have the lowest eigenvalue
2<_)(k 0) l
e2¢tr/a - i{(1 +/z2)MH (k0) + I~M~2(ko) - ,/[(1 - / ~ 2 ) M H(k0) +/aM~2(k0)] 2 + 8/~2M~3(k0)2}
The related eigenvector can be obtained from (4.7.26)

~<_) = ½{(1 -/,/2)Mll (ko) -k-//M12(ko) + ,/[(1 - #2)M H(ko) + #Mlz(ko)] 2 + 81~12M13(ko) 2 }
//<_) = 2#M,3 (ko) (4.7.27)
It follows from eq. (4.7.22c) that
a(1, ko) l ~1_!)
-~ at k0=(~22.
a(3, ko)
As was shown above, the interaction energy is minimized if the eigenvector
ooo(P, ko)=O<_)(p, ko) from (4.7.26b) is proportional to the amplitudes, a(p, koj) from
(4.7.22c). It occurs if
• <_) = a(1, ko) --: 1 (4.7.28)

//<_) a(3, ko) 2
The calculation of the sums by means of the Ewald method °5) gives
MH(ko) = - 1.74, m,3(ko) = - 1.26, M~2(ko) = 0 (4.7.29)
Vanishing M~2(ko) simplifies eq. (4.7.27):
~<_) = ½{(1 - ~2)M~, (ko) + ,/[(1 - ~2)M,l (k0)f + 8 M . (ko) 2}
//~_) = 2/~M13(ko). (4.7.30)
Substituting (4.7.30) into (4.7.28) yields
1 -- . 2 M l l ( k o ) J [ 1 --/~2 M l l ( / O ) 1 2 + 1 ,
(4.7.31)
4u M,3(ko) ~ 4-~/ M,3(ko)J 2=2"
The positive solution of eq. (4.7.31) with respect to # is:
Ml~(ko) /l- Ms~(ko) T
i (4.7.32)
/z = P° -- 2MI1 (ko) k
Substituting the numerical values (4.7.29) into (4.7.32) gives
eoct
# =/~0 = - - -~ 1.425. (4.7.23)
etetr
The calculated ratio of the charges #0 --- 1.425 is quite close to the ratio 3 = 1.5 of valencies
for trivalent and diavalent ions. The 5% deviation may be attributed to a well known effect,
deviation of effective charge of a ion from its integer valency.
Therefore, we derived that trivalent ions, M" = M +3, should occupy the octahedral
sublattice and divalent ions, M'--M+% should be in two tetrahedral sublattices. The
stoichiometric formula (4.7.6) then reads
(MI~ ~ [-1,/2) [M1/8
+2 I'X-]7/8][M1/8
+2 [~]7/8] O . . . .~/I+31~A'+2r~
,/z "",/4 "-'
or
M+2M+304 . (4.7.34)
These calculation results are in complete agreement with the structure observations. In the
spinel, MgA1203, divalent Mg ions do occupy the tetrahedral sublattice whereas trivalent A1
ions are distributed over the octahedral sublattice in accordance with the distribution function
(4.7.21).
Compounds with the stoichiometric formula (4.7.34) and the structure depicted in Fig. 33
are very widespread as native minerals and oxides synthesized in laboratories. All of them
belong to the spinel-type structure named so after spinel, MgA1204.
5. CONCLUSION
Summing up the foregoing we should emphasize that the proposed approach regards a
ceramic compound as an interstitial ordered phase in the bcc, fcc or hcp solid solution, the
order-disorder transition being situated above the melting point. The order-disorder
transition and disordered parent phase cannot be thus observed. In fact, for most oxides,
halides, chalcogenides and other compounds, disordered interstitial solutions have not been
observed. The latter raises the question, whether the hypothetical disordered parent solution
has any physical meaning or it is merely a mathematical abstraction. The predicting power
of the theory of ceramic crystals based on consideration of ordering in the interstitial parent
solution is the most convincing argument in favor of the parent phase concept. But just
recently this concept has received very strong confirmation. The fast neutron irradiation of
spinel, ZnFe204, NiFe204 resulted in disappearance of some reflections in the diffraction
pattern. Remaining reflections are related to the fcc disordered solid solution whose crystal
lattice parameter is twice as small as the spinel crystal lattice parameter. (54'55)The formation
of the disordered solution is caused by irradiation-induced disordering of interstitial Zn and
Fe atoms along octahedral and tetrahedral sublattices of the fcc host lattice composed of
oxygen atoms.
The same effect could, for example, be expected in the cases of the bcc-based rutile
structure, TiO2, and homologous phases, Ti,O2,_ 1. The irradiation-induced disordering in
these structures is supposed to result in disappearance of reflections in the diffraction pattern
other than those related to the disordered bcc parent solution. These effects would be caused
by disordering of Ti atoms along the bcc host lattice formed by oxygen atoms.
Treatment of chemical compounds as completely ordered solid solutions enables us to
associate into large groups those phases whose structures look absolutely different but whose
parent disordered state proves to be the same. Such an association is not a formal procedure.
It reveals the profound generic relation between various quite different structures. It enables
us to determine the orientational relations between phases and mechanism of phase
transformations, for example, at oxidation-reduction processes.
The latter can be exemplified by consideration of formation of a homologous phase,
Ti.02,, _ I'
U,
r.~
,.-]
Table 4. Stable Predicted Superstructures and the Examples of Corresponding Observed Compounds
(1) Superstructures in the BCC Host Lattice. Octahedral Site Occupancy
Stoichiometric Distribution Structure
7.
t-'
r~
Composition Formula Function n(R) Types Examples of Compounds
I II 1II IV V
MO [M]O (3.2.22) NaCI MgO, CaO, BaO, FeO, CoO, NiO, TaO, SrO
MO [Mi/2[] i/2][M 1/2[] i/2]° (3.2.46) NiAs VS, FeS, MnTe, NiS, CoS, NiSe, CoTe, NiTe
MO2 [Mr/4 [~3/4][MI141"~3/4]O (3.2.68) rutile, TiO2 TiO2, SnO2, GeO2, SiO2 (stishevite), MnO2,
NbO2, MOO2, ReO2, WO2, OsO2
IrO2, (FeSb)O4, (TaFe)O4, (TaV)O4
(CaSb)O,, (A1Sb)O,
MO2 [MI/4[~3/4][Mt/41~3/4]O (3.3.22b) ct-PbO2 ct-PbOz, Ti02, high pressure, wolframites:
(MnW)O4, (FeW)O4, (CoW)O4, (MgW)O,,
(Nbln)O4, (FeNb)O4, (FeTa)O4 (FeNb2)O6,
FeTa206
M203 [MI/31~2/3][MI/3 D2/3]O (3.3.47) 0~-A1203, corundum A1203, Fe203, Cr203, Ti203, Rh203;
ilmenites: (MnTi)O3, (FeTi)O3, (NiTi)O3,
(MgTi)O3, (ZnTi)O3, (LiTa)O3
M~Oz._ ~ [Mn/2(2n_l)[~(3n_2)12(2 n ~)][M./2~z,_l)[]~3._2)/~2. i)]0 Magn61i phases Ti,O~_~ (3~<n ~<10)
VnO2~_l (3~<n ~<8)
Formulae inside brackets show the relation b~tween interstitial M atoms and their vacancies, l-q, in the Ox and Oy octahedral site sublattices.
(2) Superstructures Based on the Tetrahedral Site Occupancy of the fcc Host Lattice
I II III IV V
MO, [O][O]M CaF2 CaF2, SrF2, BaF2, CdF2, CeO2, ThO:,
fluoride ZrO 2 and HfO: (at high temperatures); Li20,
Na20, K20, Rb20
MO [O][lk-llM (4.2.6) ZnS ZnO, high pressure
MO [O1/2[] 1/2][O 1/2[] i/2]M (4.2.9) PtS PtS, PtO, PdO, CuO, AgO
MzO [O~/~1~/4] [Ov~[]3/4]M (4.2.10) Cu20 Cu20, Ag20
M203 [O3/4[]t/4][O3/41x-ll/4]M antiisomorphic to (4.2.10) Sb203 Sb203, As203
MO lOt/2 [~1/2]{01/2[] I/2]M (4.2.16) PbO PbO, SnO, antiisostructural phase Li(OH)
M203 [O3/4[] i/4][O3/4Ix-'i/4
l ]M (4.2.24) 5C203 C-type of oxides Ln203(Ln-Gd-Lu) >
Y202, 1n203, Sc203, Mn203 >
M7012 [06/Tf-X-ll/.t][Oo/rlk-ll/7]M (4.2.35) UY6OI2 UY6OI2, Ce7012, Tb7Oi2, Pr7Ot2, Sc4Ti30,2 ,.4
etc. (see Table 3) r~
M~M~'O7 [07/81-X-II/s][O7/sf~j/s](M'I/2M'I)2) (4.3.31), (4.3.44) pyrochlore Ln2R207 (Ln is a rare-earth element, R = Z r , ~¢
Hf, Ti, Sn). More than 500 compounds with
this structure are known >
,'4
MO 2 [M,:s []7:sl[M,:s []7:8](O,:~ Dr:2) (4.3.31b), (4.3.44) cristobalite, SiOz SiO2, BeF2, (AIP)O 4, (BP)O4, (BAs)O4,
(MnP)O4 7~
M'M"O4 [(M~/2M~/2)l/4[]3/4][M~/2M'{/2)I/4[]3/4]O (4.3.46) sheelite, CaWO 4 CaWO4, ZrSiO4, YPO,, BaWO4, PbWO 4,
KReO4, CaCrO4 O
-n
[], vacancies in tetrahedral sites; I--I, host lattice vacancies.
rn
(3) Superstructures Formed by Simultaneous Ordering of Interstitial Atoms over Octahedral Sites and Vacancies over the fcc Host Lattice Site:. >
I II III IV V
MO 3 (Ikql/,IO3/,j)(Mi/,~E]3/4) (4.5.7) ReO 3 ReO 3, WO 3, Mo(OF2), Nb(O2F)
MM'O 3 (M]/403/4)(Mt/4[]3/4) (4.5.7) CaTiO3, perovskite CaTiO 3, BaTiO3, SrTiO3, YFeO 3, YAIO3
M~O3._l (I-~(n_lF2(2n_l)O(3n_l)/2(2n_l))(Mn/2(~_l)l-q(3n_lF2(Z,~_~)) Magn61i phases V:Os, MosO23, (Mo, W)10029, (Mo, W),O32, ,~
(Mo, W)14041
~ , host lattice vacancies; t~, vacancies in octahedral sites.
L.O
L~
The conventional structure interpretation of these compounds is based on the crystal-

lographic shear mechanism(13) which seems to be sufficiently artificial and does not have the
thermodynamic foundation. As a matter of fact, the crystallographic shear is merely a
possible geometric mechanism of the transition between two crystallographic states. Accord-
ing to this mechanism, the complicated aggregates of oxygen vacancies in the rutile structure,
TiO 2, result in the shear of various parts of the crystal with respect to each other which
eventually gives the homologous phase structure.
On the contrary, according to the superstructure concept formulated in this paper,
homologous phases are just long-period bcc-based interstitial ordered phases where inter-
stitial Ti atoms form ordered distribution over octahedral interstices of the bcc host lattice
composed of O atoms. Such a concept gives a more realistic interpretation of reduction of
the rutile structure. During reduction process, the O atom frame in the bulk of the rutile
structure is assumed to be invariable. The reduction reaction involves only surface O atoms
which react with reductant and leave surface layers. Remaining Ti atoms diffuse from the
surface inside the bulk of crystal increasing the content of Ti atoms in octahedral interstices.
As a result, the Ti atom distribution is reordered to fit new stoichiometric composition and
to minimize the interaction energy. The reordering yields the long-period superstructure
corresponding to a homologous phase. It is noteworthy that in most of studies of
nonstoichiometry in the rutile structure, the existence of interstitial atoms rather than oxygen
vacancies are reported.
In this review the phases derived from the bcc and fcc interstitial solid solution have been
considered. The crystal structure determination was based on two procedures, the symmetry
analysis reducing the number of possible structures to a few ones and the interaction energy
analysis yielding the final stable structure fitting the valencies of constituents and stoichiomet-
ric composition. In the symmetry analysis the maximal amplitude principle was utilized,
whereas in the interaction energy analysis the spectrum of the characteristic matrix of the
interaction energies was examined.
The striking result of this consideration is coincidence of the observed structure of almost
all bcc-based and fcc-based binary and pseudo-binary oxides with the structures predicted by
the relevant theory. Table 4 demonstrates the agreement between the theoretical predictions
and observed structures. It gives the list of the theoretically predicted oxides and correspond-
ing real oxides with the same atomic structure. One may see that each derived stable
superstructure has many real examples.
The question why the maximal amplitude principle formulated in purely geometrical terms
proves to be the efficient tool in the crystal structure determination deserves some more
discussion. Let us recall that the maximal amplitude principle implies the most stable
structures to be generated by the only star which has the form, {k0} = {51H }, {½H}, {¼H},
where H is a parent phase reciprocal vector. The latter may however occur if the minimum
eigenvalue of the characteristic matrix Vpq(k) falls on these singular vectors k 0. This
immediately raises the next question, of why the minimum eigenvalue falls on the singular
vectors {½H}, {½H} and {¼H}? This question can be answered if we recognize the fact that
the interatomic interaction energies are not constants as it was assumed in the relevant theory.
Indeed, Nature uses all possible means to reduce the energy of the system to its lowest value;
particularly it cannot neglect such an opportunity as changing interaction energies to shift
the wave vector k0 corresponding to the minimum eigenvalue to one of the singular points,
½H, 1 H or ¼H, and thus to provide substantial stepwise drop in the interaction energy.
Variations of interaction energies can be implemented by means of reconstruction of electron
band structure, polarization of atomic electron shells, heterogeneous atomic displacements
from regular points and so on. Shift of the k0 vector to the singular points in the reciprocal
lattice can be also achieved by homogeneous host lattice distortion.
In some rare occasions, when all these effects cannot nevertheless bring the point k0 related
to the minimum eigenvalue to one of the singular points, {½H}, {1 H} or {1 H}, a homologous
phase is formed. Then the maximal amplitude principle works in a different way--the stable
structure of a homologous phase is achieved by means of maximizing the dominant wave
amplitudes at the expense of amplitudes of nondominant waves which in this case cannot
however be reduced to zero (see Section 2.5). Such a situation occurs when the main
contribution to interatomic interaction energy is provided by long-range interactions,
conduction electron effect caused by resonance interaction of concentration wave with the
Fermi surface, (56) strain-induced interaction (s) and so on.
In any case the observations show that most of ceramic compounds, sometimes very
different by their chemical nature, are really crystallized in accordance with the maximal
amplitude principle. It enables us to regard this principle as quite universal and thus to
consider it a powerful tool in the theoretical determination of the structure of crystals.
ACKNOWLEDGEMENTS
I am extremely grateful to Prof. D. E. Laughlin of Carnegie-Mellon University and Prof.
J. W. Christian of the University of Oxford who found time to edit the manuscript and make
many valuable remarks.
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Progress in Materials Science Vol. 29, pp. 1-138, 1985 0079-6425/85 $0.00 + .

CONCENTRATION WAVE APPROACH IN

A. G. Khachaturyan* and B. L Pokrovskiit

4.2.3. Structures obtained by refinement o f the model 91

The review is addressed to graduate students and researchers in physical metallurgy,

1. CONCENTRATION WAVE REPRESENTATION OF THE STRUCTURE OF INORGANIC

1.1. Representation of Completely Ordered Phases in Terms of Static Concentration

n(p, R) = ~ a(p, k) exp(i2rckR) (1.1.1)

n(p, R) = cp + ~' a(p, k) exp(i2r~kR) (1.1.5)

~, v~(p, k )v*(p, k') = 6o~'rkk' (1.1.9)

n(p, R) = ~ ?~(k)~p~k(p, R) = ~ ?~(k)v~(p, k)exp(i2rrkR) (1.1.10)

a ( p , k ) = y' ?,(k)u~(p,k). (1.1.11)

~ y,,(k,)oo,(p, kl) ~,,(kz)o~,,(p, kz) exp(i2r~(k, + kz)R)

= ~,gTk?,(k)?*,(k') No p,, q~,k(P, R)q~k, (p, R)

The chain of equalities (1.1.18) proves the summation rule (1.1.15).

1.2. Concentration Waves and Diffraction

Ahost(q) =~fhost(q)exp(--iqr) =fhost(q)~exp[--iq(R + u(R))] (1.2.2)

Ai,t(q) = ~ f, nt(q) exp(- iqr) (1.2.3)

aint(q ) = E fint(q )rt (p, R ) e- ~q(R+ hp

=fint(q) ~ e-'hp~ n(p, R) e -iqR. (1.2.5)

A(q) =Ao~t E e-i'*+fi.t ~ e-'. E n(p, R) e -'R (1.2.8)

Aint(q) =fint ~ e-i'h' ~ 7~(k)uo(p, k) ~ e'~kR e -iqR

=fint E e-iqhP E 7a(k )Oa(p' k) E e-i(q-2'~k)R" (1.2.10)

A(q) = (Aint(q))¢=2n(H+k)-----Nof i n t ~ e -~2n(H+k~p ~

Correspondence between concentration waves and diffraction patterns proves to be

2. STABILITY OF STOICHIOMETRIC COMPOUNDS

~ Wpq(R -- R')~p~k(q, R') = 2,(k)~p~k(p, R) (2.1.3)

V*(k ) = ~ Wq,(R) e a"kR = ~ Wpq(-R) e i2nkR

~-"2 Wpq(R') e -i2nkR' : Vpq(k ). (2.1.8)

The chain of equalities in (2.1.8) proves the Hermitian conditions (2.1.6).

v.(k)-,~ v,2(k) ... v~v(k)

v*v(k ) v*~(k ) vw(k ) - ,~

,~,(k), ,~2(k),... ,~(k),... ,L(k)

E = ½N0 ~ 2~(k) I y~(k) 12 (2.1.10)

2.2. The Maximal Amplitude Principle and Dominant Waves

Nint being the total number of interstitial atoms.

in eq. (2.2.1). The result is

Substituting the left-hand side of eq. (1.1.15) for c in (2.2.2) we have

fundamental reciprocal lattice vector H being assumed to be identical). This degeneration is

G~s, = ~g,(kj,)j, = -cl ~. t ?,(kj,) 12 (2.2.7)

is always present. In eq. (2.2.10)

v,,(o) v,2(0) v,2(o)...v,2(o)~

consisting of v rows and v columns• The corresponding eigenvalue is

L.c/v when p=v

ndom(p, R) = c + ~ ?~0(kjs0)v~0(p' kj~o) ea,%oR' (2.2.17)

c_: + Z I Yoo(k,~o) I ~ - c. (2.2.18)

2.3. Stability of Layer Structures

[ndom(P, R)] s~ = + y,o(ko)o,o(p, ko) e '2~k°" + ?*o(ko)o,o(p, ko)* e -i2~k°R (2.3.2)

where Sl is the minimum integer for which the equation

a(p, sko) = ~ y~(sk )vo(p, sko). (2.3.6)

It follows from the definition (1.1.3) that

a(p, (s, - s ) k o ) = a(p, - sko). (2.3.9)

2.4. The M o s t Stable Layer Structures with Fixed Stoichiornetry

one of two functions

Substituting (2.4.7) into (2.4.8), we have

n(p,R)=~+~ cos~HR +sin HR . (2.4.9)

3ko = (7~ 97 ~ ) = (73~7 7I ) + (022)--,(~- -~I 7)

2.5. The Nature of Homologous Series of Chemical Compounds

l o(kj o) l 2 = 21 T 0(k0) 12 (2.5.2)

because y~0(-k0) = y*0(k0).

Substituting (2.5.6) into (2.3.5), we have

n(p, R) = %(m) = ~ ap(s) exp i sm (2.5.9)

Cpst = ap(0) - ~ ' m°

vv(k ) v~(k ) vw(k ) - ,~

[ndom(P, R)] s~ = + y,o(ko)o,o(p, ko) e '2~k°" + ?o(ko)o,o(p, ko) e -i2~k°R (2.3.2)