Spectral Symmetry in Lattice Dynamical Models: J. List. Maths Applies (1968) 4, 375-398

J. List.
Maths Applies (1968) 4, 375-398
Spectral Symmetry in Lattice Dynamical Models

R. J. BELL AND P. DEAN
[Received 9 November, 1967]

Conditions are derived for the existence of symmetry in the squared frequency spectra
of lattice dynamical models, and it is shown that the displacement eigenvectors associated
with symmetrically related frequencies are simply related. It is also demonstrated that in
some cases a delta function exists in the spectrum in addition to the symmetry related
regions: the modes associated with the delta-function are vibrations in which certain
atoms remain stationary. Various applications of the theory are discussed.
1. Introduction
ONE of the obvious features of the spectra of many lattice dynamical systems is the
symmetry or near-symmetry of the squared-frequency distribution function. Although
the literature abounds in references to this symmetry (or its absence) for particular
systems, there has been no investigation of the general conditions for the existence of
symmetry, or of the possible significance of exact or near-symmetry in an observed
or calculated spectrum. In this paper we present a theoretical study of the problem.
Some of our results complement the work on sum rules and interatomic forces by
Brout (1959), Rosenstock (1963, 1965) and Rosenstock & Blanken (1966).
One of the main results of our study is the derivation of conditions under which
spectral symmetry will occur. However, this is by no means the only significant
result which emerges. We find, for example, that displacement eigenvectors corresponding to conjugate (i.e. symmetrically placed) squared frequency values are simply
related. We can show when a band-gap will occur, and can predict the existence in
some cases of a ^-function singularity in an otherwise symmetric spectrum. Our
results hold not only for the full squared frequency spectrum, but also for the squared
frequencies associated with any phonon wave vector in a regular lattice. The study
of systems with irregular boundaries leads to the remarkable result that, for certain
classes of disordered systems, the degree of localization of vibrational modes at high
frequencies is exactly reproduced in the low frequency region.
The plan of this paper is as follows. In Section 2 we present the basic mathematical
theory: we establish that the eigenvalues and vectors of matrices of a particular type
have certain symmetry properties. In Section 3 we relate this analysis to the equations
of rigid-ion lattice dynamical systems, deriving the physical conditions which lead to
spectral symmetry. In Section 4 we discuss the effects of boundary conditions. Section 5
concerns the application of the theory of this paper to a range of simple regular lattices.
In Section 6 we derive some interesting properties for a certain class of disordered
systems. We consider extensions of the conditions for symmetry in Section-7.
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376
We emphasize one important point at this stage. The symmetric spectra we shall
discuss in this paper are squared-frtquency spectra Gico2), where Giafydco2 represents
the proportion of squared frequencies of the system which lie in the infinitesimal
interval co2 to ofi+dco2. The function Gico2) is related to the frequency spectrum ^(cu)
by the simple formula Gico2) = gico)l2co.
(1)
where C is &p x q matrix of rank r and O is its hermitean conjugate, u and v are column
vectors of orders p and q respectively, and the I's are unit matrices of appropriate
orders. The constants a and b are real, so that M is hermitean and its eigenvalues k
are real. Lanczos (1958) has considered the more restricted eigenvalue problem in
which a = b = 0.
Decomposing (1) we have immediately the relations
Cv = ik-a)u,
(2a)
Ctn = ik-b)v.
(2b)
Premultiplying the first of these equations by O , and the second by C we obtain
C+Cv = y2v,
(3a)
C O u = y2a,
.
(3b)
where the eigenvalues y2 of O C and C O are given by
y2 => ik-a){k-b).
(4)
It can be shown that the matrices O C and C0 are each of rank r, and they possess r
simultaneous eigenvalues y2 > 0. Except in the case p = q = r there is one remaining
eigenvalue, y2 = 0, which occurs with multiplicities pr and qr for C O and O C
respectively.
It is not possible, in general, to satisfy the eigenvalue equation (1) merely by
combining an arbitrary solution of (3a) with a solution of (3b). In order to analyse the
structure of the eigenvectors of M in detail, we shall find it convenient to separate
the cases (i) k # a or b; (ii) k = a # b; (iii) k = b # a and (iv) k = a = b.
(i) k j a or b
One may solve (3a) to obtain r solutions v (corresponding to the positive eigenvalues y2) and then find the appropriate a's from (2a); alternatively, one may use (3b)
to obtain the u's, and then construct the v's from (2b). Let us examine the latter
situation, having found a y2 and a corresponding u from (3b). It is evident from (4)
that each y2 corresponds to a pair of eigenvalues,
k = \{a+b[ia-bY+Ay2^},
(5)
of the original equation (1). For both these values of k we can use (2b) to obtain v.
If one choice of sign in (5) gives an eigenvalue k and eigenvector (u, \) of (1), the other
choice corresponds to the eigenvalue k' and eigenvector (u'.v7) where
;.' = a+b-k;
\
u' = (A-fl)n,
v' = ib-ky,.]
2. Mathematical Basis
In this section we shall investigate the solutions of the eigenvalue equation
LATTICE DYNAMICAL MODELS
377
This may readily be verified by substitution. The paired vectors (u,v) and (11',/)
constitute 2r solutions of (1) with A ^ a or b. We shall refer to such pairs of eigenvectors, related by (6), as conjugate eigenvectors.
In the case where A # a or b is a multiple eigenvalue associated with L linearly
independent eigenvectors
(u,,vi),
/ = 1,2,...,L
associated with multiple eigenvalue A' = a+b X. However, if the former vectors
are chosen to be mutually orthogonal, the latter are not necessarily so unless a = b.
(ii) A = a # b
From equations (2) we obtain
Cv = 0,
(7)
Oil = (a-b)v,
(8)
so clearly, for non-trivial solutions, we require u # 0. Now the well-known compatibility theorem for linear operators (cf. Lanczos, 1958) states that (8) is solvable
if and only if the right-hand side is orthogonal to all solutions of the adjoint homogeneous equation Cw = 0. Gearly, this condition can only hold in the present
context if v = 0, so the eigenvectors (u,v) of (1) must be given by
v = 0,
C u = 0,
(9)
there being pr such solutions. It is clear that we cannot obtain paired eigenvectors
of M from (6) in this case.
(iii) A = b = a
The argument for A = b is analogous to that in case (ii). The eigenvectors of M
are now given by
u = 0,
Cv = 0;
(10)
in this case there are qr such solutions. The transformation (6) again gives n', v' = 0,
showing that the eigenvectors cannot be paired.
(iv) A = a = b
The results given for cases (ii) and (iii) provide a full solution to (1) even when
a = b. Now, however, the eigenvectors of (1) need not be restricted to the form (u,0)
or (0,v); we can obtain the p+q2r required vectors in the more general form (u,v)
by combining appropriate solutions of Du = 0 and Cv = 0.
Summarizing, for A # a or b, the eigenvalues of (1) occur in conjugate pairs A and
A' = a + b?.; the corresponding conjugate eigenvectors are related by the simple
transformation (6). This part of the eigenvalue spectrum of M is symmetrical about
the point i(a+b). If p> r there are also eigenvectors (u,0) corresponding to A = a
and if q > r there are vectors (0,v) corresponding to A = b; these vectors do not occur
in conjugate pairs related by (6). Finally, as an important additional point, we note
from (5) that there is a region between a and b where no eigenvalues of M can occur.
then the application of (6) to these leads to a set of L linearly independent vectors
378
= kY' { ( l - e ^ R ^ + e a - R ^ ) } . ( r ^ - r j
(A atoms),
(lla)
= * ' {(l-e)ft,ft /l ,+8(l-ft,.ft,.)} . ( r . - r , )
(5 atoms),
(lib)
where the primed summations are restricted to nearest neighbours. In equations (11),
ia and TP denote the vibrational amplitudes of A and 5-atoms, ft^ is the unit vector
in the direction of RI/t and 1 is the d x d unit dyadic.
With the introduction of mass-dependent amplitudes
(12)
and the identification ofi X, equation (11) may be written in the hermitean form
(13)
where the vectors U and "V are themselves composed of {/-component vectors sa
and Sj, and the elements of M are dxd symmetric dyadics. <<f will often be a sparse
matrix, whose dyadic elements are non-zero only if a and /? are nearest neighbours,
when they take the form
= -^m^-HO-e^R^ + ea-R.A,)}.
04)
si and Si are diagonal matrices with dyadic elements
-VU)}.
-ft/.A)},
(15)
where the primed summations are restricted as in equations (11).

If the equilibrium configuration of the system is such that
.*. = el,
St,, = M,
(16a)
(16b)
t For the sake of generality we take the nearest neighbours of A to mean simply those atoms
which interact directly with A. In most cases considered (but not all) these are the atoms which are
spatially nearest to A.
% We denote the central and non-central force constants by (1 e)k and dc, respectively, to ensure
that the entire range of central to non-central force constant ratios can be covered by varying the
single parameter e between 0 and 1.
3. Application to Lattice Dynamical Systems

Consider a system in J-dimensions consisting of two types of atoms A and B, with
respective masses mA and mB. Suppose that each ^4-atom has nA nearest neighbours,!
all of type B, and each i?-atom has nB nearest neighbours, all of type A. (We include
also systems of identical atoms, in which case the separation into types A and B is
purely formal.) We denote the equilibrium position vectors of .4-atoms and 5-atoms,
respectively, by R, and R, (a,/? = 1,2,3,...) and define RJ/5 = R^-R,.
Let the forces between nearest neighbours be harmonic in character, with central
and non-central force constants (l-e)fc and ek respectively.J The time-independent
equations of motion for a normal vibration about equilibrium, with frequency co,
are then
379
it is clear that (13) assumes exactly the form of equation (1) of Section 2. It then follows
that the symmetry properties described in Section 2 apply to the atomic vibrations
of the dynamical system. For (16a) and (16b) to be valid, we require
kQ. -2e) ' ft,/,ft^ = (mja-kenjl,
(17a)
*(1 -2e) ' , . , . = (mj-kenjl,
(17b)
a = {l + (d-2)e}knA/dmA,
b = {l+(d-2)e}knBldmB,
(18a)
(18b)
since
Tr{fta/,fta/,} = l.
Conditions (17) are equivalent to specifying that each A-atom resides in a spherically
symmetric potential VA(r) (in ^-dimensions), and each B-atom in a spherically symmetric potential Vgfj), when the nearest neighbours are heldfixedin their equilibrium
positions.
Equations (17) are trivially satisfied for any system with equal central and noncentral force constants (e = %). In this case
]
if a and ft are nearest neighbours |
(19)
= 0, otherwise
J
and we can reformulate the problem as one of motion in one-dimension, by adopting
solutions of the form sa = sjt, sf = spi where i is a convenient unit vector. This
transformation enables us to reduce the order of the dynamical matrix by a factor of
1/d, the reduced matrix being simply related to the adjacency matrix of the system
(cf. Busacker & Saaty, 1965). The spectrum remains invariant under arbitrary
distortions of the system provided the topology, force constants and atomic masses
are not changed. This property, for e = i, provides a method for investigating the
effect on the spectrum of the topology of the system, as distinct from the geometry.
If the atoms of a system lie in a hyperplane of dimension less than d, the out-ofplane components of H^ are zero; thus for (17) to hold (apart from the trivial case
e = $) we must either discard the out-of-plane equations from (11) and consider only
motion within the hyperplane, or vice versa. Thus, in the case of the one-dimensional
linear chain, equations (17) are satisfied if we consider longitudinal motion only,
or transverse motion only, but (in general) not both together.
Equations (17) simplify considerably for two-dimensional structures, many of which
form useful illustrative systems (cf. Sections 5 and 6). Consider a typical A-atom of
a two-dimensional system, surrounded by nA 5-atoms. Let 9^ be the angular coordinate of Sa/J in a plane polar co-ordinate system in the plane of the atoms. The
unit vector fta/J then has Cartesian co-ordinates (cos 9^, sin 9^), and the conditions (17)
are equivalent to
' exp 2i9xf = 0,
(20a)
/0, a = O,
(20b)
which, in turn, imply that
380
implying
m^siX-aXX-B) = mjjn^l-aW-b),
(4a)
where
mAa = mAa,
mB5 = ntgb,
and a, b are given by (18). Thus, once the spectrum has been calculated for any
finite mass-ratio, the spectrum for any other mass-ratio can immediately be deduced
from (4a).
For any given v4-atoma, let us now renumber its nearest neighbours by /? = l,2,...nA.
Then a simple choice of 0,^'s which satisfies (20a) is given by
0*i, = 0a+pnnJnA,
0 = l,2,...nA (nA^2).
(22a)
With a corresponding renumbering (a = l,2,...nB) for the neighbours of any given
5-atom, f}, we find (20b) satisfied by
Op. = Qf+annplriB,
a = l,2,...nB
( f l >2).
(22b)
Equations (22) are valid for any integers na and nf prime relative to nA and nB,
respectively. The presence of the arbitrary constants 6t and 0f merely reflects the
rotational invariance of conditions (17). More generally, equations (17) are satisfied
if the nearest neighbours of each atom can be partitioned into several sets, each of
which obeys an equation of the type (22a) or (22b). Equations (22) and their generalization imply the circular symmetry of the potential at each atom when its neighbours
are heldfixedin their equilibrium positions.
Applying the results of Section 2 to systems of the type considered above (i.e. which
satisfy equations (17)), we find that (i) no frequencies occur in the range a<oJ1<bt
(ii) there may be special vibrations at a? = a and aP = b, in the former case only
,4-atoms vibrate, while in the latter only .ff-atoms vibrate, (iii) the remaining squared
frequencies are distributed symmetrically about ofi = $(a+b), i.e. they occur in
symmetric (conjugate) pairs co2 and co'2 such that aP+co't = a+b, and (iv) the vibrational amplitudes associated with a symmetric pair of frequencies are related by the
simple formula (6).
It is appropriate, at this stage, to comment on a consequence of our choice of force
constants. By denoting the central and non-central force constants by (1 e)k and sk,
respectively, we have ensured that the entire range of central to non-central force
constant ratios can be covered by varying the single parameter e between 0 and 1.
A result of this parametrization, for two-dimensional structures having spectral
symmetry, is that the lattice parameters a and b are independent of s; for twodimensional systems, therefore, the position of the centre of symmetry, and the
positions of any predicted band gap or 5-function are independent of e. This
simplification does not occur, however, for systems in three or more dimensions.
We conclude this section by describing another important property of systems
with spectral symmetry, namely the variation of the spectrum with atomic mass.
Let X = aP- be a squared frequency of the system with masses mA and mB, and 1 = cS2
be the corresponding squared frequency for masses fhA and fnB. It follows from equations (4), (14) and (15) that
381
Finally, if (r^r,,) are the vibrational amplitudes for a mode with squared frequency
?. when the masses are mA and mB, the corresponding amplitudes (ra,r?) for masses fnA
and mB are given by
f . = <a>
h = /J,
where
a I* = mA{_k-a)lmA(l-a) =
mJI-h)lmB(k-b).
4. Boundary Conditions
The dynamical systems encountered in solid state physics are often so large on the
atomic scale as to comprise, effectively, an infinite number of atoms. Clearly, for these
systems the eigenvalue problem of equation (1) would be quite intractable without
some means of first reducing the equations of motion. One approach is to compute
the vibrational properties, not of the whole system, but of a representative sample
containing a reasonably large but finite number of atoms. A method of imposing a
boundary condition is to consider atoms outside the sample as fixed in their equilibrium positions (without changing the values of any force constants); this constitutes
the well-known rigid-wall boundary condition. Another boundary conditionthe
free-end conditionis obtained by severing the bonds (i.e. forces) connecting atoms
within the sample to those outside. In Section 4.1 we shall show that the imposition
of the rigid-wall boundary condition on a sample of atoms in a lattice dynamical
system does not alter the features of spectral symmetry we have already discussed,
provided the original system satisfies the two conditions of Section 3; on the other
hand, the imposition of the free-end condition does, in general, destroy the spectral
symmetry of a model. In Section 4.2, we shall consider the effects of the important
cyclic boundary condition.
4.1. The Rigid-wall and Free-end Conditions
Consider the situation where one of the atoms, say the /ith atom of a lattice
dynamical system, is held fixed in its equilibrium position. We take account of this
in the system of equations (11) by setting rM = 0 and discarding the /zth (dyadic)
equation. The effect on (13) is simply to remove the /ith row and column of dyadics
from the dynamical matrix M (and the /zth vector amplitude sM from the amplitude
eigenvector). If the dynamical matrix is originally of the form in (1), the process of
removing rows and the corresponding columns leaves this form unaltered. Thus, a
system which satisfies the conditions for spectral symmetry again satisfies those
conditions if one atomand, therefore, any number of atomsare held fixed in their
equilibrium positions.
If the free-end boundary condition is imposed upon a sample of atoms in a system,
it is clear (from equations (11) and (15)) that not all the diagonal elements of s4 and Si
will now take on the values a and b (cf. equation (16)), respectively. The free-end
sample of atoms will therefore not, in general, satisfy the conditions for spectral
symmetry.
To summarize, if we have a large (or infinite) system of atoms which satisfies the
conditions for spectral symmetry, and we restrain any number of these atoms to remain
An important consequence of this relation is that, if localized modes occur for systems
with spectral symmetry, the degree of localization is independent of the atomic masses.
382
4.2. The Cyclic Boundary Condition and Reduced Dynamical Matrix

If the dynamical system is an infinite regular lattice, the cyclic boundary condition
may be imposed in order to reduce the number of degrees of freedom. In applying
this well-known condition one considers only a unit cell of the lattice, assuming that
the vibrational amplitudes have a plane-wave-like spatial variation, differing only
in phase from cell to cell. The full dynamical matrix of the original system then
condenses (cf. for example, Dean, 1967) to a reduced dynamical matrix Uifjj(k) whose
order is the number of degrees of freedom in the unit cell, and whose elements are
functions of a wave-vector k; it is usual to allow k to take values in a region of
reciprocal space known as a Brillouin zone.
Specifically, for a lattice vibration with wave-vector k, an equation such as (13)
for the original systemreducesto
where the subscript R indicates that we are now dealing with reduced matrices and
vectors, ^ ( k ) and ^ ( k ) contain k-dependent complex phase factors, arising from the
interaction between A and B atoms in neighbouring unit cells. If the system satisfies
the conditions of Section 3, $iK and 3SR contain no phase factors, since neither A nor B
atoms interact with atoms of the same kind: thus if, as indicated in Section 3, &/ and SS
are of the form a\ and b\ respectively, sfR and 88R take exactly these same forms,
although, of course, their orders are substantially smaller.
Provided, then, that the conditions for spectral symmetry apply to the lattice as
a whole, (23) may be written as
^UwJ - Icwoi "bi'jL(k)J - W ) J '
(24)
which is of the form (1). Consequently, our analysis and theorem of the preceding
sections applies not only to the full dynamical matrix and the total squared frequency
spectrum, but also to the set of squared frequencies associated with each wave-vector k.
This result is complementary to the sum rules discovered by Brout (1959), Rosenstock
(1963,1965) and Rosenstock & Blanken (1966).
5. Spectral Symmetry of Regular Lattices
In this section we consider the spectral symmetry properties of a number of regular

structures, drawing upon results in the literature where possible. In 5.1 we describe
in their equilibrium positions, the resulting system will also satisfy the conditions
for spectral symmetry. On the other hand, if we isolate a sample of atoms from the
original system by severing bonds between the atoms of the sample and those outside,
the sample will not, in general, constitute a system which satisfies the conditions. Of
course, the effect of any particular boundary condition becomes less important as the
size of the sample to which it applies increases. Thus, very large samples may well
exhibit almost exact spectral symmetry even under the condition of free-end boundaries;
this point is clearly of importance, for free-end boundaries probably simulate quite
closely the surfaces of real solids.
383
the longitudinal vibrations of the linear chain, and refer briefly to its transverse
vibrations and general vibrations in ^-dimensions. Several regular two-dimensional
structures are discussed in 5.2: we consider the quadratic and hexagonal lattices, and
a lattice of triangular molecules which illustrates particularly clearly some of the
concepts introduced in Section 3. In 5.3 we discuss the spectral symmetry of some
common crystal structures.
Consider a linear chain of N atoms, with nearest-neighbour forces, and subject to
(say) the rigid wall boundary condition. The time independent equations of motion
for longitudinal vibrations are
-mpP-X; = k(xj_i-2xj+xJ+1),
j = 1,2,... N
(23)
xo = xN+i = 0,
where ntj is the mass and Xj is the amplitude of vibration from equilibrium of the^th
atom, and k denotes the (central) force constant between nearest neighbours.
Suppose, now that all the even-numbered atoms are ^4-atoms with mass mA, and
all the odd-numbered atoms are B-atoms with mass mB. To recast the equations in
the form of the matrix relation (13) we simply re-order the atoms so that the evennumbered equations are written first, and then we apply the transformation (12) with
ra s jca and r? = xf. It is clear that interactions occur only between unlike atoms,
and that each atom resides in a symmetric (i.e. even) potential when its nearest
neighbours are held in their equilibrium positions; therefore this system, the alternating
diatomic chain, satisfies the conditions of Section 3 for spectral symmetry. We find
that the lattice parameters a and b (cf. equations (16), (17) and (18) of Section 3,
with e = 0) are given by
a = 2klmA,
b = 2k/mB.
From the theory of Section 2, there follows at once the well-known result that the
squared frequency spectrum is symmetric about the point co* = (k/mA+klmB), and
that a gap exists between ufi = 2k/mA and ofi = 2k/mB (cf. for example, Maradudin
et a]., 1963, p. 62). If N is odd, the B atoms outnumber the A atoms by one, and we
note (again from Section 2) that there will be an additional frequency (that is, in
addition to the symmetric spectrum) at ufi- = b = 2k/mB.
Another interesting feature of the system follows from the conjugate eigenvector
property discussed in Section 2. If we consider the atomic displacements in a particular
mode (with squared frequency aP, say), the displacements in the conjugate mode (with
squared frequency 2k/mA+2k/mBa)Z) are given simply by multiplying the displacements of one species of atom (either even or odd) by a negative constant which depends
only on co2- and the lattice parameters (cf. equation (6) of Section 2); if o& refers to
an acoustic mode, the conjugate mode lies in the optical band, and vice versa. This
property is illustrated in Fig. 1, where the horizontal scale refers to the positions of
atoms along the chain, and the vertical scale to the atomic displacements.
In the special case mA = mB = m, the system reduces to a monatomic chain and
the lattice parameters take the values a = b = 2k/m; we therefore find a spectrum
which is symmetrical about co2 = Ikjm, but we do not predict a band gap. The
5.1. The Linear Chain
384
Acoustic mode
Fio. 1. Diagram illustrating the conjugate eigenvector property. Atomic amplitudes in the two
cases are related by equation (6) in the text.
We now consider the general vibrations of linear chains in d-dimensions, and include
non-central forces between nearest neighbours. The equations of motion can be
decoupled into d independent systems by resolving the motion (i) along the direction
of the chain and (ii) along (d 1) mutually orthogonal directions perpendicular to the
chain. The system of equations arising from (i) gives a squared frequency spectrum
which is symmetrical about o 2 = (l e)(k/mA+k/mB), whereas each of those arising
from (ii) gives a spectrum which is symmetrical about co2 = e(k/mA+k/mB) (in the
notation of Section 3). Clearly, while the spectrum for longitudinal vibrations alone,
or for transverse vibrations alone, is symmetric, the combined spectrum for general
vibrations will be symmetric in general if and only if 6 = . This a particular example
of the general condition that, for our theorem to apply to a multi-dimensional system,
the potential at each atom in the equilibrium configuration must have full spherical
symmetry over all the dimensions of motion.
5.2. Two-dimensional Lattices
Here we consider the spectral symmetry of a number of regular two-dimensional
structures. Five well-known planar lattices are shown in Fig. 2: they are (a) the simple
quadratic, (b) the hexagonal, (c) the triangular, (d) the Kagom6 and (e) the four-eight
lattice. Of these, the triangular and Kagome lattices cannot be divided into two types
of sites in the required way (cf. Section 3), and neither the Kagomd nor four-eight
lattices satisfy the criteria (20) for circularly symmetric potentials. The remaining
systems both obey the conditions laid down in Section 3 for spectral symmetry:
well-known spectrum for the monatomic chain is indeed of this form (cf. for example,
Maradudin et aJ., 1963). A point of interest for this system is that the conjugate
eigenvector property (cf. Fig. 1) still applies between modes lying in the two halves of
the spectrum (i.e. 0<afl<2kjm and 2klm<o>*<4k/m), despite the disappearance
of the band gap; thus one might, with some justification, refer to "acoustic" and
"optical" regions of the single-band spectrum.
There is ample evidence that the introduction of longer-range forces into the
monatomic and alternating diatomic linear chains destroys the symmetry of the
0)2-spectrum (cf. Rosenstock, 1958; Czachor, 1963). Again, we note that a linear chain
with a more complex unit cell (such as AAB or ABC) does not, in general,
have a symmetric squared frequency spectrum (Maradudin & Weiss, 1958; Pozubenkov,
1966).
385
'f '
(a)
(b)
/
/\
(c)
X X XX
:xxx >
xxx x
(x x x >
(d)
(e)
FIG. 2. Five two-dimensional lattices. The simple quadratic and hexagonal lattices satisfy the
conditions for spectral symmetry. The triangular, Kagomd and four-eight lattices do not.
symmetric about o 2 = (klmA+k/mB), and a spectral gap between ofi = 2kjmA and
a)2 = 2k/mB (in the notation of Section 3). In the monatomic case (mA = mB = m),
the squared frequency spectrum will be symmetric about cu2 = 7k\m. If out-of-plane
(rather than in-plane) vibrations are considered, the spectrum is again symmetric
(and, in the alternating diatomic case, has a band-gap). It is clear that a general motion
of the system (containing vibrational components both within and perpendicular to
the system) will, in general, lead to a symmetric spectrum only in the case where
central and non-central force constants are equal (i.e. e = i).
Montroll (1956) has studied the dynamics of the monatomic simple quadratic
lattice, with nearest-neighbour interactions only, and his formulae show the G(a>2)
function to be symmetric for all ratios of the central to non-central force constants.
Simple quadratic lattices with second as well as first neighbour interactions have been
studied by Montroll (1947) and Bowers & Rosenstock (1950); it is clear from their
results that the introduction of second-neighbour forces destroys the symmetry of
the G)2-spectrum.
The Hexagonal Lattice. The two-dimensional hexagonal lattice (depicted in Fig. 2(b))
provides a dynamical system which satisfies the conditions of Section 3, if only
these structures, the simple quadratic and hexagonal lattices, are discussed below.
We consider also the vibrational spectrum of a lattice of triangular molecules which
illustrates particularly clearly some of the properties predicted in Section 3.
The Quadratic Lattice. We consider the in-plane vibrations of the quadratic lattice
(monatomic or alternating diatomic) depicted in Fig. 2(a), a system which satisfies
the conditions of Section 3 if interactions are restricted to nearest neighbours. With
force constants defined as in equations (11), a and b take the same values as for the
longitudinal vibrations of the linear chain, so we again predict an co^spectrum
386
FIG. 3. The "molecular-triangular" lattice.
on the atomic vibrations of glasses. This structure, which illustrates particularly

clearly some of the features predicted by the theory of Sections 2 and 3, is depicted in
Fig. 3: the unit cell, which is outlined by broken lines in the figure, contains two
^4-atoms (denoted by O) and three 5-atoms (denoted by ) . We regard nearest
nearest-neighbour interactions are allowed. According to equation (21) of Section 3,

the lattice parameters for in-plane vibrations are
a = 3kl2mA\
b = 3k/2mBj '
so we predict a spectrum which is symmetric about to2 = 3(k/mA+klmB)/4 and
which has a gap between up- = 3k/2mA and co2- = 3k/2mB. A similar result holds for
the entirely out-of-plane vibrations.
Dean (1963) has considered the in-plane vibrations of the monatomic hexagonal
lattice. Hefindsa symmetric squared-frequency distribution, consisting of two distinct
bands which just touch at the mid-point of the spectrum, as well as two symmetrically
placed 5-functions (one at the bottom and one at the top of the continuous
spectrum) each of which contains exactly one quarter of all the normal frequencies of
the system. These ^-functions must be regarded as spectral bands of infinitesimal
width, and are not to be confused with the 5-functions arising from the existence
of unequal numbers of A- and i?-type lattice sites. The out-of-plane motion of this
system was described in an earlier paper by Hobson & Nierenberg (1953), who found
a symmetric squared-frequency distribution. Their spectrum (suitably scaled) is
identical to that derived by Dean for the in-plane vibrations, but without the <5functions. The work of Rosenstock (1953) indicates that the inclusion of longer-range
interactions destroys the symmetry.
The Molecular-triangular Lattice. We now describe the dynamics of a twodimensional structure which has been of some interest to us in connection with work
387
so the squared frequency at which only B-atoms vibrate is given by co2 = k\mB.
The rest of the spectrum will be symmetric about ofi = (3kl4mA+kl2mB), and will
contain no squared frequency between 3k/2mA and k/mB.
e = 0 or1
ri
S)
/ N.
Fio. 4. Histograms of squared frequency spectra for the molecular-triangular lattice. The arrows
indicate the positions of 8-functions.
We have computed the squared frequency spectrum of this system for the case
mA = 2, mB = 1, k = 1 for a range of values of e (where, in the notation of Section 3,
(1 e)k is the central and sk is the non-central force constant). The normal frequencies
were determined by direct diagonalization of the 10x10 reduced dynamical matrix,
26
neighbours (which are not, of course, necessarily geometrically nearest neighbours)

as pairs of atoms which are joined by full lines in the diagram; with this convention,
interactions between like atoms do not occur. The three nearest-neighbour bonds at
each /4-atom are separated by angles of 2n/3, and the two at each 5-atom by an angle
of 7i/2, so that each atom resides in a circularly symmetric potential when its nearest
neighbours reside in the equilibrium position (cf. equations (22) of Section 3). The
system thus satisfies the criteria of Section 3 for spectral symmetry.
An interesting feature of the structure is that the B atoms outnumber the A atoms by
three to two: thus in addition to a symmetric squared frequency spectrum we expect
to find at co2 = b a <5-function containing 20% of the total number of squared
frequencies. We note from equations (21) that the a and b values for this lattice are
given by
a = 3k/2mA,}
(26)
b = k/mB,
388
taking a total of 576 wave-vectors (k-values) in the Brillouin zone. The squared
frequency distributions are shown as histograms in Fig. 4, in which the vertical
arrows represent 5-functions. The <5-function at ofi = k/mB = 1 contains 20%
of the frequencies, as anticipated, and the remainder of the spectrum is clearly
symmetrical about co2 = (3k/4mA+k/2mB) = J. As predicted, no squared frequencies
FIG. 5. Vibrational amplitudes of the molecular-triangular lattice for a "8-function" mode at

>= 1. The A-atoms (O) remain at rest.
- 2
2 -
Ikl
FIG. 6. a2-k relations for the molecular-triangular lattice for the direction [0,1] in the Brillouin zone.
389
5.3. Three-dimensional Structures

We find that many of the common crystal structures satisfy the conditions of Section
3. There are, however, some surprising exceptions: thus, whereas the simple cubic and
body-centred cubic systems have spectral symmetry, the face-centred cubic does not.
In the face-centred cubic structure, atoms at the centres of faces are connected not
TABLE 1
Some common crystal structures which (a) conform and (b) do not conform
to the conditions for spectral symmetry if only nearest-neighbour interactions occur
(a)
(b)
Simple cubic
Body-centred cubic
Diamond
Sodium chloride
Caesium chloride
Zinc blende
Fluorite (CaF2)
Wurtzite
Face-centred cubic
Hexagonal close packed
only to nearest neighbours at the cube vertices, but also to atoms on adjacent face
centres, and therefore the system does not satisfy the first criterion of Section 3,
i.e. that interactions occur only between unlike atoms. In Table 1, we list a number
of the common crystal structures which satisfy, and others which do not satisfy, the
conditions for spectral symmetry if only nearest neighbour forces are taken into
occur between 3k/2mA and k/mB, i.e. between J and 1. However, except for the case
e = i , the actual band gap is wider than our predicted one; this is particularly
noticeable for e = 0 and 1, where the continuous regions of the spectrum have
contracted into <5-functions. Although our theory leads to the actual band gap for
the majority of common structures, it is worth stressing that for some special lattices,
such as the present example, our prediction (which simply gives a region devoid of
frequencies) may represent a gap smaller than that which actually occurs.
We computed the vibrational amplitudes for one of the modes with squared
frequency to2 = 1 (in fact, the mode with wave vector k = 0): the result is shown
for the case e = 0 in Fig. 5, in which the directions and relative magnitudes of atomic
displacements are indicated by arrows. As our theory predicts, for modes whose
frequency lies in the <5-function, only the 5-atoms are in motion. In Fig. 6, we
give the dispersion curves (a*2 versus k) for the direction [0,1] in the Brillouin zone.
Apart from the horizontal line at a>2 = 1 (which contributes to the 5-function),
the remaining branches lie symmetrically about afi- = %. This demonstrates our
conclusion of Section 4, that spectral symmetry occurs not only for the full squared
frequency distribution, but also for those squared frequencies associated with any
wave vector k.
390
a = 2[l+(d-2)e]k/mA,\
b = 2[l+(d-2)s]k/mBJ
so we predict a squared frequency spectrum which is symmetric about
[l+(d-2)e](k/mA+k/mB),
and has a gap between 2[l+(d-2)e]k/mA and
2[l + (d-2)e]k/mB. Montroll (1956) has calculated the squared frequencies for a
J-dimensional NxNx...xN
cubic array of identical atoms, with rigid wall
boundaries and nearest neighbour interactions. Our prediction is clearly consistent
with his result,
where m is the atomic mass and, in the notation of Section 3, ki = Jfc(l e) and
k2 = k$ = ... = kx = ke are the central and non-central force constants, respectively.
It is worth noting that, when there are more A atoms than there are 5-atoms (or
vice versa), i.e. when N is odd, Montroll's formula gives modes at
in agreement with our predictions (for the <5-function modes).
The Body Centred Cubic Lattice. Another crystal structure which satisfies the
conditions for spectral symmetry, if only nearest neighbour interactions occur, is the
body centred cubic lattice in its monatomic or diatomic (CsCl) form. The lattice
parameters for the diatomic case are
a = S(l + e)k/3mA,\
b = 8(l+e)k/3mBJ
so here we expect a squared frequency spectrum which is symmetric about the point
CD2 = 4(l + e)(klmA+k/mB)l3, with a band gap between ofi- = 8(1 + e)k/3mA and
consideration. We shall specifically consider the spectral symmetry properties of the

simple cubic, body-centred cubic, and CaF2 (fluorite) structures.
The Simple Cubic Lattice. The cubic lattice (monatomic or alternating diatomic),
with nearest neighbour forces, is the simplest three-dimensional structure which
satisfies our conditions for a symmetric spectrum. The lattice parameters for the
diatomic structure are (in the notation of Section 3):
a = 2(l + e)k/mA,\
b = 2(1+ e)k/mB;f
it follows that the spectrum is symmetrical about co2 = (1 + e)(k/mA+k/mB), and
shows a band gap between up- = 2(1 + e)k/mA and aP- = 2(1 + e)k/mB. All this is
consistent with the exact formulae for the spectrum, as derived by Maradudin et al.
(1958). The monatomic case mA = mB has been treated in detail by Montroll (1956)
who finds that the spectrum is symmetric for all ratios of the central to non-central
force constant, a result which is again to be expected from the theory of Section 3
above. Work by Rosenstock & Newell (1953) on the monatomic lattice, and by
Mazur (1958) on the diatomic lattice, confirms that the spectral symmetry is lost if
second-neighbour forces are included.
For the generalization of the diatomic cubic lattice to ^-dimensions, the lattice
parameters are
391
y
b = 8(l + e)A:/3mJ
'
Lattice dynamical models of CaF2 studies in the literature, to date, have included
longer range forces than those between nearest neighbours, so the exact spectral
symmetry of the simple force model is not apparent. However, we note here that, if
only nearest neighbour forces are considered, the squared frequency spectrum for this
structure will be symmetric about co2 = (l + eX2fc/3m^+4fc/3mB) and there will be
no squared frequencies between 4(1 + e)k/3mA and 8(l + e)fc/3mB; in addition there
will be a 5-function at afi- = 4(1 + e)k/3niA corresponding to normal modes in
which only the fluorine atoms vibrate.
6. Systems Lacking Spatial Periodicity

In the previous section we considered examples of regular lattices with spectral
symmetry. Here we shall be concerned with the application of the theory of Sections 2
and 3 to systems which lack overall spatial periodicity.
It is clear from the discussion of boundary conditions in Section 4.1 that the
symmetry properties described in Section 3 apply not only to a range of regular
lattices, but also to structures which include isolated fixed atoms or clusters of fixed
atoms and, further, to finite or infinite clusters of vibrating atoms bounded by rigid
walls of fixed atoms. Three two-dimensional structures containing these features are
illustrated in Fig. 7, in which the fixed atoms are represented by unoccupied lattice
sites, the A atoms by open circles (O) and the B atoms by closed circles ( ) .
As a particular example, let us consider the structure shown in Fig. 7(c). This system
obeys the equations for a circularly symmetric potential, and there are no forces
between atoms of the same kind. The lattice parameters are the same as those for the
regular diatomic quadratic lattice discussed in Section 5, viz.
a = 2k/mA
b = 2k/mB.
We therefore expect a squared frequency spectrum which is symmetric about the
point co2 = k(jn2l+mBl)
and which has no frequencies between co2 = 2k\mA and
a>2 = 2kjmB. Since there are 13 4-atoms as compared with 7 5-atoms, the matrix C
0)2 = 8(1 + e)k/3mB. We have not found, in the literature, any exactly calculated
spectrum for the monatomic or diatomic cases. However, Rosenstock (1955) has
investigated the spectrum for the monatomic structure, via the critical points, and
found that the critical points lie symmetrically about the mid-point of the spectrum.
Although Rosenstock's sketch of the a)2-distribution (top diagram of Fig. 11 of his
1955 paper) appears to have an overall asymmetry, Rosenstock has stated (pers.
comm.) that errors occurred in the actual preparation of the figure, and that the
spectrum should be "entirely symmetric about the center point".
The Fluorite Structure. The fluorite lattice is interesting in that it contains unequal
numbers of two atomic species, and also satisfies the conditions for spectral symmetry
when only nearest neighbour forces are considered. The lattice may be regarded as
a body-centred cubic structure, with the cube vertices (A-type sites) occupied by
fluorine atoms and alternate body centres (5-type sites) by calcium atoms; according
to equations (18), therefore, the relevant parameters are given by
392
of equation (1) has dimensions p = 26 by q = 14, and at least 12 of the 40 squared

frequencies will occur at 2k/mA. (More precisely, if there are n squared frequencies
at b = 2k/mB, there will be 12+n at a = 2Jc/mA.)
We computed the frequencies and eigenvectors for this system when mA = 2,
mB = 1,1c = 3, e = $ (where, as stated in Section 3, (l-e)k is the central, and ek
, J
(b)
(c)
FIG. 7. Structures with irregular boundaries. Provided the missing atoms in this diagram are regarded
as fixed and the forces between the vibrating atoms and the fixed atoms are not altered in any way
(rigid-wall boundary condition) these structures satisfy the conditions for spectral symmetry.
FIG. 8. The squared-frequency spectrum of the system of Fig. 7(c) for the case mA = 2, ms = 1,
k = 3, e = i (n\A denotes the mass of an atom represented by O (A atoms), ms the mass of an atom
represented by (S atoms)).
(a)
(b)
(0
FIG. 9. Vibrational amplitudes for three modes of the system of Fig. 7(c). (a) and (b) represent
conjugately related modes at u2 2-07 and uA = 6-93, (c) represents a mode of the special S-function
at ca2 = 3; note that in this mode the S-atoms remain at rest.
,I
*
(a)
, J
393
THEOREM. If a monatomic dynamical system obeys the conditions of Section 3 for

spectral symmetry then, neglecting the zero frequency modes associated with infinitely
heavy atoms, the corresponding isotopically disordered system satisfies the conditions
for spectral symmetry in the limit of infinite mass ratio. If the infinitely heavy masses
are unevenly distributed between A- and B-type sites, an additional 5-function, corresponding to modes in which atoms at either A- or B-sites remain stationary, will occur in
spectrum.
This result promises to be of some interest in the theory of isotopically disordered

systems, in view of the remarkable connections which have already been established
between the spectra of lattices with finite and infinite mass ratio (Borland, 1964;
Hori, 1964; Matsuda, 1966). It is already known (cf. Domb et al, 1959) that the
squared frequency spectra of one-dimensional systems of this kind (i.e. disordered
Final level
(fixed)
11
12
1 3
Second level
First level
Root point
(fixed)
FIG. 10. Illustration of the second-order Cayley tree of branching-ratio 3.
two-component linear chains with infinite mass ratio) are symmetric, and there is
evidence in the literature (Fig. 7(e) of Pay ton & Visscher, 1967) that the same is
true of similar two-dimensional systems.
An interesting one-dimensional aperiodic system, to which our theory of Section 3
applies, is the Cayley tree considered by Rubin & Zwanzig (1961). In this system
the non-central force constant). The squared frequency spectrum is shown in Fig. 8
as a "stick" diagram. The symmetry about co2 = kim^+mg1)
= f is evident, as is
the "band gap" between 2k/mA(= 3) and 2k/m^= 6); also, 12 squared frequencies
occur at co2 = 3. The vibrational amplitudes are displayed in Fig. 9 (the arrows
indicate the directions and relative magnitudes of atomic displacements) for the
conjugate modes at co2 = 207 and aP- = 6-93, and also for one of the "5-function"
modes at o = 3. Figure 9(a),(b) demonstrates clearly the conjugate eigenvector
property described in Section 2, while from Fig. 9(c) we note once again that only
the more plentiful species of atom vibrates at the special frequency co2 = 3.
Consider, now, the case where atoms located at A and B sites in a system containing
also fixed atoms are, in fact, of the same kind. The two-component isotopically
disordered structure in which one component has infinite mass is a system of just this
type. We therefore arrive at the following result:
394
a = b = k(m+l).
We thereforefindthat the squared frequency spectrum i s symmetric about co2 = k(m +1),
a result which may be verified by referring to Rubin & Zwanzig's calculated spectrum.
For an Mh order tree, the total number of atoms is given by
N(A)+N(B) = (m*-l)/(m-l),
while the difference between the numbers of the two types of atoms is
\N(A)-N(B)\ = (m*- l)/(/n +1), N even
= (mN+l)/(m + l), iVodd;
the proportion of modes having the special squared frequency co2 = k(m+1) is therefore
/=
N even
m+1
This is in agreement with the result

/->( (
I as N-* co
given by Rubin & Zwanzig.

Our results for the Cayley tree can easily be generalized to the case where mA # mB
and where the branching ratio is different for odd and even levels. Moreover, the
occurrence of spectral symmetry and special frequencies persists when arbitrary
branch-points are taken to be fixed, and even when the tree is "pruned" at some of
these fixed branch points.
Finally, it is worth noting that for m = 1 the Mh order Cayley tree becomes a
linear chain of N atoms with fixed boundaries, and the even and odd levels are just
even and odd points along the chain. The occurrence of spectral symmetry for the
linear chain has already been discussed in Section 6.
a trunk runs from the root-point (0) to thefirst-levelbranch-point (1) where it divides
into m parallel branches; each of these m branches then itself splits into m sub-branches
at the second level branch-points (l,i), and so on. The number of interior levels is
called the order of the tree, while m is called the branching ratio. A second-order
Cayley tree, with branching-ratio 3 is illustrated diagrammatically in Fig. 10.
The root-point and final level branch-points of the Cayley tree are considered fixed,
and the interior branch-points are taken to be particles; the branches are regarded as
springs constraining the particles to their equilibrium positions. Suppose that the
particles are permitted to move in a direction parallel to the springs; then the tree
represents a system vibrating in one dimension. If we take the branch points on odd
levels to be y4-atoms and those on even levels to be 5-atoms, it is evident that only
AB interactions occur. In addition the potential is symmetric (because of the onedimensional nature of the system), so the system satisfies the conditions of Section 3
for a symmetric spectrum. Considering, for simplicity, the case mA = mB = 1, the
lattice parameters (cf. Section 3) are
395
7. Extension of the Conditions for Spectral Symmetry
In Section 2 and 3, we proved that spectral symmetry occurs for a dynamical system
if (i) the atoms can be classified into two types such that interactions only occur
between unlike atoms and, (ii) each atom resides in a spherically symmetric harmonic
potential when the remaining atoms are in their equilibrium positions. Our theory,
of course, applies directly (like most physical theories) to idealized models rather than
real systems. It applies, for example, to many common crystal structures (as we
noted in Section 6) provided interactions are limited to nearest neighbours. In real
solids, on the other hand, second- and higher-neighbour interactions are always
present to some extent, leading inevitably to the violation of condition (i). In spite of
this the theory has a relevance to real solids. If second- and higher-neighbour contributions represent only a small perturbation of the dynamical matrix, and the
unperturbed system (with nearest-neighbour forces only) is one which satisfies the
conditions for spectral symmetry, it is a reasonable hypothesis that the perturbed
system will retain some features of this symmetry. Indeed, the departure from ideal
symmetry may be regarded as a measure of the relative importance offirst-and higherneighbour forces. The persistence of near-symmetry, when a small proportion of
second-neighbour force is included, is clearly borne out, for example, by the theoretical
work of Bowers & Rosenstock (1950) and Rosenstock (1953, 1955).
Many lattice dynamical models, while not directly satisfying the conditions of
Section 3, can easily be decoupled into systems which do possess spectral symmetry.
One simple example, already discussed in Section 5, is the linear chain vibrating in
^-dimensions; here the longitudinal and transverse vibrations separately provide
symmetric spectra. Another, less obvious, example is the diatomic lattice (with
nearest neighbour central forces) depicted in Fig. ll(a). By a simple transformation
of co-ordinates, the dynamical matrix for this system can at once be partly diagonalized
to yield 30% of the squared frequencies; these frequencies, at o 2 = 0, correspond to
modes in which the iJ-atoms move perpendicular to their nearest neighbour bonds. The
remainder of the dynamical matrix is of the form (1), with a = 3k/2mA, b = 2k/mB
andp = 4q/3. The lattice will therefore have 30 % of its squared frequencies at co2 = 0,
10% (corresponding to modes in which only the ^4-atoms vibrate) at co2 = a and the
remainder distributed symmetrically about (a+b)/2; further, there will be a spectral
gap between ofi = 3k/2mA and ofi = 2k/mB. In Fig. ll(b) we give a histogram of the
spectrum, computed for the case mA = 2, mB = 1, k = 1, E = 0; it is clear that it
bears out our predictions. The arrows in the figure denote <5-functions; the <5functions at aP- = \ and aP = ^- each contain 10 % of the squared frequencies of the
system, while that at 2 = 0 contains 40 % (30 % of these arising from the original
decoupled modes, with 10% corresponding to those in the ^-function at co2 = ^).
A decoupling can also be performed for the model of Fig. 11 (a) with completely
non-central forces between nearest neighbours. The spectrum is identical to that for
central forces, but the decoupled modes at to2 = 0 now correspond to vibrations of
the 5-atoms along the nearest-neighbour bonds.
The cristobalite lattice, shown in Fig. 12(a), is a three-dimensional structure which
can easily be decoupled to provide a symmetric spectrum, if only central forces
between nearest neighbours are allowed. This lattice is based on the diamond structure,
with y4-atoms on the diamond sites (denoted by open circles O) and 5-atoms on the
396
mid-points of A-A lines (denoted by closed circles ) . In this case the decoupled
modes, at co2 = 0 correspond to vibrations of the .ff-atoms perpendicular to their
nearest neighbour bonds; there are two such modes for every 5-atom. The dynamical
matrix for the remaining modes is of the form (1), with a = 4k/3mA, b = 2k/mB,
vvw-
FIG. 11. Illustration of a planar lattice the equations of motion of which can be decoupled as
described in the text. The histogram represents the squared-frequency spectrum of the lattice for the
2, ma = 1, k = 1, e = 0, the arrows representing 8-functions.
(b)
(a)
(0
-k-
-s-
Fio. 12. The Cristobalitc lattice, with histograms of the squared frequency spectra for the cases
(b) rA = |, n>B = I, k = 1, e = 0 and (c) mx = f, ma = 1, k = 1, e = 1. The arrows indicate
8-function positions.
p = 3N(A) and q = Af(5) where N(A) and A^(5) are the numbers of A- and 5-atoms,
respectively. The spectrum will therefore have 2N(B) squared frequencies at co2- = 0,
3N(A)N(B) at OJ2 = 4k/3mA and the remainder symmetrically distributed about
co1 = 2kl3mA+k/mB with a gap between 4k/3mA and 2kjmB. We have computed the
(b)
397
8. Summary
We have given, in Section 3, conditions under which the squared frequency spectrum
of a lattice dynamical rigid ion model will be symmetric; we have found, also, that
in some cases an additional "special" ^-function occurs in the spectrum. For certain
systems a prescription has been given for rinding a region of the spectrum devoid of
frequencies (i.e. we have indicated a minimum band gap). We have shown that
displacement eigenvectors corresponding to symmetrically related (conjugate) squared
frequencies are simply related, as indicated in Sections 2 and 3; eigenvectors corresponding to frequencies in the special (5-function which may occur in the spectrum
have been shown to correspond to modes in which atoms located at certain sites
remain at rest. For periodic systems the theory applies to specific k-values, and thus
complements previous work on sum rules.
We have applied the general theory to various types of lattice dynamical model,
verifying results which have been obtained by other authors and predicting features
of the spectra and dynamical properties of systems which have not yet been fully
treated. The general theory has applications to simple lattice dynamical models,
to models of disordered structures (as indicated in Section 6) and to realistic crystal
structures; in this last case it suggests a simple explanation for the near-symmetry
present in some experimental spectra.
This work has been carried out at the National Physical Laboratory.
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spectrum for a sample of this lattice, subject to rigid wall boundary conditions, with
N(A) = 192, N(B) = 308, mA = f, mB = 1, k = 1 and e = 0. The squared frequency
distribution, shown in Fig. 12(b), agrees with our predictions. The 5-function at
a)2 = 2-8 contains 117 frequencies, the one at co2 = 0-8 contains 268, while that at
op = 0 contains 733 (of which 616 arise from the decoupled modes and 117 correspond
to those at ofi = 2-8).
A similar result holds for the cristobalite lattice with completely non-central forces
between nearest neighbours; one can decouple N(B) modes at co2 = 0 corresponding
to vibrations of the 5-atoms along the bonds, and the relevant parameters for the
remaining modes are a = $k/3mA, b = 2k/mB, p = 3N(A) and q = 2N(B). In this
case, therefore, there will be N(B) squared frequencies at a? = 0, 2N(B)-3N(A) at
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with a gap between Sk/3mA and 2k/mB. This is borne out by the squared frequency
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same as before).
398
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Spectral Symmetry in Lattice Dynamical Models: J. List. Maths Applies (1968) 4, 375-398

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Spectral Symmetry in Lattice Dynamical Models: J. List. Maths Applies (1968) 4, 375-398

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J. List.

Maths Applies (1968) 4, 375-398

Spectral Symmetry in Lattice Dynamical Models

[Received 9 November, 1967]

Mathematics Division, National Physical Laboratory,

R. J. BELL AND P. DEAN

LATTICE DYNAMICAL MODELS

R. J. BELL AND P. DEAN

= * ' {(l-e)ft,ft /l ,+8(l-ft,.ft,.)} . ( r . - r , )

si and Si are diagonal matrices with dyadic elements

where the primed summations are restricted as in equations (11).

3. Application to Lattice Dynamical Systems

LATTICE DYNAMICAL MODELS

*(1 -2e) ' , . , . = (mj-kenjl,

which, in turn, imply that

R. J. BELL AND P. DEAN

LATTICE DYNAMICAL MODELS

R. J. BELL AND P. DEAN

4.2. The Cyclic Boundary Condition and Reduced Dynamical Matrix

^UwJ - Icwoi "bi'jL(k)J - W ) J '

In this section we consider the spectral symmetry properties of a number of regular

LATTICE DYNAMICAL MODELS

5.1. The Linear Chain

R. J. BELL AND P. DEAN

LATTICE DYNAMICAL MODELS

R. J. BELL AND P. DEAN

FIG. 3. The "molecular-triangular" lattice.

on the atomic vibrations of glasses. This structure, which illustrates particularly

nearest-neighbour interactions are allowed. According to equation (21) of Section 3,

LATTICE DYNAMICAL MODELS

neighbours (which are not, of course, necessarily geometrically nearest neighbours)

R. J. BELL AND P. DEAN

FIG. 5. Vibrational amplitudes of the molecular-triangular lattice for a "8-function" mode at

LATTICE DYNAMICAL MODELS

5.3. Three-dimensional Structures

R. J. BELL AND P. DEAN

consideration. We shall specifically consider the spectral symmetry properties of the

LATTICE DYNAMICAL MODELS

6. Systems Lacking Spatial Periodicity

R. J. BELL AND P. DEAN

of equation (1) has dimensions p = 26 by q = 14, and at least 12 of the 40 squared

LATTICE DYNAMICAL MODELS

THEOREM. If a monatomic dynamical system obeys the conditions of Section 3 for

This result promises to be of some interest in the theory of isotopically disordered

FIG. 10. Illustration of the second-order Cayley tree of branching-ratio 3.

R. J. BELL AND P. DEAN

This is in agreement with the result

given by Rubin & Zwanzig.

LATTICE DYNAMICAL MODELS

7. Extension of the Conditions for Spectral Symmetry

R. J. BELL AND P. DEAN

LATTICE DYNAMICAL MODELS

BORLAND, R. E. 1964 Proc. phys. Soc. Lond. 83, 1027.

R. J. BELL AND P. DEAN

DEAN, P. 1967 / . Inst. Maths. Applies. 3, 98.

HORI, J. 1964 Prog, theor. Phys. Osaka 32, 471.

MONTROLL, E. W. 1947 / . chem. Phys. 15, 575.

E. W. 1956 Proc. 3rd Berkeley Symposium on Mathematical Statistics and

PAYTON, D. N. m & Visscher, W. M. 1967 Phys. Rev. 154, 802.

POZUBENKOV, A. F. 1966 Soviet PhysicsDoklady (Translation), 10, 600.

ROSENSTOCK, H. B. & BLANCKEN, G. 1966 Phys. Rev. 145, 546.

RUBIN, R. J. & ZWANZIG, R. 1961 / . math. Phys. 2, 861.

A. A., MONTROLL, E. W. & WEBS, G. H. 1963 Theory of Lattice Dynamics in