The Transfer Matrix Method in The Theory of Normal Vibrations of Chain Molecules

Supplement ot the Progress of Theoretical Physics, No.
23, 1962
The Transfer Matrix Method in the Theory of

Normal Vibrations of Chain Molecules
Hirotsugu MATSUDA
Department of Chemistry, Kyoto University, Kyoto
Downloaded from http://ptps.oxfordjournals.org/ at Pennsylvania State University on May 12, 2016

After reviewing the transfer matrix method introduced by Schmidt, and by Hori
and Asahi for the problem of the vibration of a disordered linear chain, we discuss
its extension by Yamamoto, Okada, and the present author to more complex systems.
Classifying the frequency regions by the 's-value', which is defined as half a number
of eigenvalues with absolute value 1 of the transfer matrix, we study the general
aspects of normal modes in each region. When s=l, a 'phase shift' is shown to be
a very useful quantity for expressing end effects on the frequency and intensity of
the infrared absorption of a chain molecule. As an application we discuss the analysis
of the experimental data on the rocking-twisting modes of normal paraffins, which
indicates the practical importance of our theory.
§1. Introduction
Various methods have been proposed and developed to study frequency
spectra of disordered lattices. Among others we may mention the Green's
function method developed by Montroll and Potts/> the moment-trace method
by Domb, Maradudin, Mazur, Montroll, and Weiss, 2>and what might be called
the negative-factor-counting method*> by Dyson, Bellman,3 > Schmidt/> Dean,
and Martin. 5>
The transfer matrix method was introduced by Schmidt4> and by Hori
and Asahi 6 > to treat the problem of the vibration of a disordered linear
chain. This method, which is also used in the problem of electronic
states of a disordered linear chain, 4>. 7 > essentially consists in transferring the
knowledge at one end up to the other end through the repeated operations
of matrices called transfer matrices. Although this method has not been
very successful in the case of finite concentrations of impurities, it has been
shown to be simple and tractable in the case of a finite number of impurities.
It is especially suited for investigating the wave forms of normal vibrations,
which are important in the problem of the infrared absorption.
The linear chain, however, is too simple as a model for studying the
infrared absorption of chain molecules on which numerous experiments have
been made. 8 > On the other hand, most quantitative theoretical analyses so far
undertaken of the experimental data were essentially based on the assumption
of the perfect translational symmetry. 9 >.Iol But this assumption is not always
*l This method is reviewed by Hori 15) in this issue.
The Transfer Method in the Theory of Normal Vibrations 23
correct.
Rosenstock 11 > has pointed out theoretically the importance of the end
effect on the intensity of the infrared absorption even when the chain is
infinitely long. The systematic infrared experiments of chain molecules with
finite lengths have been made by Snyder12 > on normal paraffins. Theimer13l
has studied the end effects on the infrared absorption of n-paraffins by the
perturbational approach, but the validity of this approach might be questioned.
In these circumstances, Yamamoto, Okada, and the present author14 J have
attempted to extend the transfer matrix method in such a way that it is also
applicable to chain molecules. This extension, which is made possible by the

introduction of auxiliary coordinates, gives a systematic prescription for the
quantitative analysis of the infrared absorption of chain molecules. Moreover,
it can be shown under what conditions some of the characteristic features
of the normal vibration of a simple linear chain persist to hold in more
complex systems. It is also of interest to investigate what kinds of new
features will appear when we proceed from a simple model to more complex
and realistic ones.
When the number of impurities in the system is finite, a finite amount
of calculation leads, in principle, to the exact answer according to our
prescnptwn. But when there are an infinite number of random impurities,
other mathematical techniques are required in addition to our prescription.
In order to treat such cases, Hori 6 J discussed the average eigenvalue
equation obtained by taking the ensemble average of the eigenvalue equation
over the random distribution of impurities. The use of the average eigen-
value equation is justifiable when almost all the systems of the ensemble
have the same eigenfrequencies. This, however, is very improbable since
he has shown for one-dimensional isotopic random lattices that the average
of the square of the eigenvalue equation diverges as the number of atoms
becomes infinite.
Actually the average eigenvalue equation gives the frequency distribution
of a virtual regular lattice, which is quite different from that of the real
random lattices in the region of higher frequency. Hori tried to improve
this by combining it with the moment-trace method, but he failed to
reproduce the fine structures in the frequency distribution obtained by Dean
and Martin 5> by a machine calculation. Therefore, the average eigenvalue
equation has, if any, only a limited range of applicability.
On the other hand, Schmidt4> set up the integral equation. Although
he started with transfer matrices, his result is similar with Dyson's and may
rather be classified as a negative-factor-counting method reviewed by Hori15>
in this issue.
Thus at present there is no proper transfer matrix method to treat the
case of an infinite number of impurities, so that we shall not discuss such
cases in the following.
24 H. Matsuda
In §2 the transfer matrix method for a simple linear chain will be

presented. The effects of the deviation from the translational symmetry on
the normal mode of the linear chain will be discussed. Although the
principal idea of this section is due to the works of Schmidt and of Hori
and Asahi, considerable reformulations and generalizations will be made so
as to be useful as a basis for later sections.
In §3 the extension of the transfer matrix method to general chain
molecules will be formulated. In §4 the important properties of the transfer
matrix will be pointed out. We shall introduce the 's-value', by which the

frequency regions of a chain molecule are classified. In §5 and §6 the
general aspects of end effects of chain molecules will be discussed.
In Appendix I, for an illustration of the practical application of our
theory, we shall discuss the analysis of the experimental data of the infrared
absorption of n-paraffins. In appendix II we shall give two models which
have some qualitatively different features from a simple linear chain.
§2. The transfer matrix method for a simple linear chain

Consider a chain of N masses, each coupled to its nearest neighbors by
elastic springs obeying Hooke's law. Let particle number j have mass mJ.
and let its displacement from its equilibrium position be u 1 . Let the elastic
modulus of the spring between particle j and (j+ 1) be k1 . Then the
equations of motion of the system are
mi1J=kJ(um-uJ) +kJ-1(UJ-1-uJ), (j=1, 2, ···, N). (2·1)
We call such a system a simple linear chain.

If we put the time factor as exp (iwt), (2 ·1) becomes
-w 2m 1u 1 =k1 (uH 1 -u1 )+k1-l(u1- 1 -u1 ), (j=1, 2, ... , N). (2·2)
As we may assume that k 1 *-0 for j=1, 2, ... , N-1, we can solve (2·2)
for UJ+l:
um = {1 + (k;-l-w 2m;)/k;}u;- (k;-dk;)u;-1,
(j=1, 2, ... , N-1). (2·3)
Hence if we define
UJ )
(2·4)
UJ-l '
we have
(}.=2 3 ... N-1) (2·5)
' ' ' )
where
(2·6)
We call T 1 the transfer matrix of part number j. T 1 is determined by the

equation of motion for particle j as a function of the angular frequency ro.
From (2 · 5) we have
(2·7)
To proceed further we must specify the boundary condition.

(I) The cyclic boundary condition
In this case we may put
and (2·8)
Hence we may define TN and T1 by (2·6) and we have
where
HN= TNTN-1 • • . T2T1. (2·9)
In order that v 1 =FO we must have
Det[HN-1] =0, (2·10)
where 1 is a unit matrix. Since
Det HN=1,
as is apparent from (2·6) and (2·8), Eq. (2·10) is equivalent to the equation
Trace HN=2. (2·11)
This is the eigenvalue equation for the frequency ro.
(II) Fixed ends

We asssume that the particles 1 and N are coupled to the particles 0
and (N + l) respectively which are held fixed. We may put in Eq (2·2)
uo=uN+l =0. (2·12)

Then we obtain
0
). (2·13)
If we define the matrices

26 H. Matsuda
1
F=( 0
) and (2·14)
we obtain from (2 ·12) and (2 ·13)
UN+1 =A(m)ul =0, (2·15)

where
(2·16)
Here and in the following (A)ae represents (a, S)-element of a matrix A.

From (2·15) we get the eigenvalue equation
A(m)=O. (2·17)
(III) Free ends

Since in this case ko=kN=O in (2·2), the equation for UN 1s:
(2·18)
In order to define TN even in this case we introduce the auxiliary coordi-

nate UN+l and write
(2·19)
UN+! =0, (2·19')
where k~ is an arbitrary non-zero constant Obviously the simultaneous

equations (2 ·19) and (2.19') are equivalent w Eq. (2 ·18). Now from
Eq. (2 ·19) we can write
(2·20)
where
(2·21)
Using the transfer matrices defined in (2 · 6) for J = 1, 2, · · ·, N- 1, and TN

in (2·21) we obtain
0
). (2·22)
Note that
(2·23)
smce k0 =0. But we may as well write

~ ). (2·23')
where a is an arbitrary constant, since T 1F does not depend on the value

of a.
The condition (2 ·19') can be expressed as
(2·24)
which leads to the eigenvalue equation

A(w)=O, (2·25)
where
(2·26)
The only difference between this case and the previous one is in the defini-
tion of TN and T 1 .
The eigenvalue equation (2 ·11) is somewhat simpler than (2 ·17) or
(2·25), because the trace is invariant under similarity transformations. But
the boundary condition of free ends is physically more interesting, so that
in the following we shall assume this condition unless otherwise stated.
Example 1.
Consider the case where all the masses and elastic moduli are the same:
m 1 =M, k 1 =K, (}=1, 2, ···, N).
Then from (2·6), (2·21), and (2·23') we may put
~ 1 ), (}=2, 3, ···, N-1), (2·27)
-1)
0 . (2·27')
Since Det T=1 and Trace T=2-w 2 M/K. the eigenvalues of T can be
written as exp( ± iA.). where
w2 = (4K/ M)sin 2 (A/2) = (2K/ M)(l-cosA)_ (2·28)
If we put
r==exp(iA./2), (2·29)
we have
(2·30)
where
28 H. Matsuda
r-1 ) (2·31)
r ,,
r -~-1 ) • (2· 31')

-r-1
Hence
A(ro) =F 1 TNSAN- 2 S- 1 T1F
= ( T NS) 11 cs- 1Tl)ueiA(N- 2 ' + ( T NS) 12cs-1T1)21e-iA(N- 2) (2·32)

Substituting (2·27'), (2·28), (2·31), and (2·31') in (2·32) we obtain
A(ro) =2i r-r-: sin(NA.) . (2·33)

r+r
From the eigenvalue equation (2·25)
A.=mr:/N (n=O, 1, 2, ···, N-1). (2·34)
Thus we obtain the whole set of eigenfrequencies
ro=2VK/M sin(mr:/2N). (n=O, l, 2, ... , N-1). (2·34')
Generally, different part~ may have different transfer matrices But

when a majority of parts have a common transfer matrix, calling these parts
basic parts, we represent the transfer matrix by the basic transfer matrix T,
which may have a form like (2 · 27) When consecutive parts are all basic,
we call a set of these part:3 a baste region Generally a chain may have
several basic regions. In the previous example all the parts except 1 and
N belong to one basic region.
When j and k belong to a basic regwn, from (2·5), (2·27) and (2·30)
we have
(2·35)
From (2·5) and (2·30)
(2·36)
where
A1 ==e-iAk( S)u ( s-1vk)1 '
A-1 ==eiAk( S) 12( s- 1Vk)2 (2·36')
When A. is real, (2·36) represents an extended wave for a displacement

u; in the basic region We call this kind of modes of vibration extended
modes. On the other hand when A has an :maginary part (2 · 36) represents
the superposition of damping waves, so that we call such a kind of modes
damping modes.*>
It must be noted that damping modes are not necessarily localized modes,
because if there are many non-basic regwns :nserted between basic regions
these modes may resonate and form so-called impurity bands_'>.n Damping
modes may, however, be localized even if there are mfinitely many non-
basic regions as Anderson 1n discussed in the problem of the absence of spin
diffusion in certain random lattices. Conversely, a localized mode may not
be a damping mode even when we can define basic regions 'ls we shall
discuss in Example 5 in Appendix II.

From (2·28) when O<w<2vK/M no damping mode may exist, and
when w>2VK/M no extended mode may exist. In the previous example,
by (2·34) every normal mode is an extended mode. In order to show that
there actually is a case in which a damping normal mode exists, we proceed
to Example 2, where a particle at part h is replaced by an isotopic impurity.
Example 2:
k1 =K, (j= 1, 2, ···, N),
\M, (j=l=h),
m;=)M'==M(l+Q). (j=h).
Without loss of generality we may take
When h= l, we have
(2·37)
where TN, 1'1· and A are defined by 1._2·27') and (2·30), and
(2·38)
(2·39)
A simple calculation leads from the e1genvalue equation (2 · 25) to:
tan( N- ~ )A=- (2Q+ l)tan(A/2) . (2·40)
~~ there exist N real roots for A in the region 0 <A<

r.:(N-1)/(N-+ )<n:, which give N distinct values of w from (2·28).
*1 We carry on this definition to the following sections where there are in general many
'A..
30 H. Matsuda
Therefore, no damping normal mode exists if Q ~- + .
~ it can easily be shown that there exif'i N -1 rf'~ 1 roots

in the region o<;.<n:(N-1)/(N--+ ). In order to investlgale one more
root, we put
(2·41)
Then Eq. (2·40) becomes

tanf=- (2Q+ 1)tan( N-+):t. (2·42)
Hence, if (2Q+ 1)( N-+ )< - + there is a real root in the regk:1
n:(N-1)/(N-+ )<;.<n:. If (2Q-t 1)( N-+ ) < - + , Eq. (2·42) has

a purely imaginary root X Writing
l=i'o/' or ).=n:-i'o/', ('o/': real),

we obtain from (2 · 28)
m=2-.IK/M cosh('o/'/2)>2vK/M . (2·43)
Thus we have a damping norma. mode. H N';;P1, then from (2·42)

we have
'o/'=ln!Q/(1 +Q) 1. (2·44)
When h=/=1, we have
(2·45)
From A(m) =0, we obtain
-2Qtan()./2) = sin N).

cos(N-h++);. cos(h-+ );.
=tan(N-h+ ; )).+tan(h- ; );. . (2·46)
If Q~O, Eq. (2·46) has N real roots in the region o<;.<n:.

If Q<O, Eq. (2·46) has N-1 real roots in the region O<-l<n{l-
2(N_!-h)+1 }. Using (2·41) we rewrite Eq. (2·46):

- 2Qcot0/2) = sin N A (2·47)

sin(N-h++)x sin(h- ; )x
If Q2:-Nj{4(h-+ )(N-h++ )}, Eq. (2·47) has a real root in the
region n{1- 2 (N_:h)+ 1 }<A<n, whereas if Q<-N/{4(h-+)(N-h
+ ; ) } , it has a purely imaginary root X. When N';?> 1 and h = O(N) we

obtain instead of (2 · 44)
'o/=ln ( 1-Q)
1 +Q . (2·48)
Summarizing the two cases h=1 and h=F1, we conclude that there is
a critical value Qcrlt for Q below which a damping normal mode exists and
above which there is no damping normal mode. Qcrlt is given by
N
(h=1, 2, ···, N). (2·49)
When N';P-1 and h=O(N), which several authors have considered, (2·49)
reduces to
Qcrlt = 0 • (2·49')
As we have seen in Example 1, in general the transfer matrices of the

end parts are different from those of the other parts. In nrd0;· to investigate
more general end effects let us consider the following example.
Example 3:
TJ=T, (2·50)
where N 1 and N 2 are independent of N. Putting
Rl= TN,TN,-1 .•. T2Tl' (2·51)
R2=TNTN-1 ••. TN-N2+1> (2·51')
we also assume that R 1 and R2 are independent of N.

In order to obtain A(w) we only have to replace T1 and TN by R1
and R 2 and N-2 by N-N1-N2 in (2·32):
A(w) = (R2S)n(S-1R1)ne~>-<N-Nl-N2l
(2·52)
32 H. Matsuda
When O~ro<2vK/M, A is real. Since R1 and R2 are real matrices, WE

have from (2·29), (2·31) and (2·31'):
(R2S)t;_(S- 1R1)f1 = (R2S)12CS-1R1)21. (2·53)
where A* represents a complex conjugate of A. Hence we get
A(ro) = gcos(AN+a), (2·54)

where
g=21 (R2S) 11 (S-1R 1) 11 e-wn,+n,l I , (2·55)

a=arg{ (R2S)u(S-1Rl)ue-iA<n,+n,l} . (2·55')
and argA denotes the argument of the complex number A. The quantities
g and a are the functions of ro but they are independent of N The eigen-
value equation (2 · 25) gives
A=mr/N+(+- a )IN. (2·56)
where n is an integer. Comparing (2 ·56) with (2 · 34) we see that the end
effect on the extended mode can be expressed by a phase shift ( ; --a) IN
When
ro>2vK/M, (2·57)
A can be written by (2·28) as
A=n:-i'o/'' C'o/'>0), (2·58)

where
ch'o/'=ro 2M/(2K)-1. (2. 58')
For N";;P1
hence
A(ro)=(R2S)n (S- 1Rl) 11 eo..<n-n,-N,l. (2·59)
Therefore, if the frequency ro which sat1sfies the equation

(2·60)
belongs to the region (2 ·57), it corresponds to a damping normal mode.

We conclude this section stressing the following points. When a simple
linear chain has a basic region, the whole frequency region can be divided
into two regions. In the lower frequency region only extended modes may
exist, and in the upper frequency region only damping modes may exist.
Each mode is characterized by a phase A between adjacen.t part::. in the basic
region. If all the parts except end parts belong to a basic region, the end
effects on an extended mode can be expressed by a phase shift ( +-o)/ N
introduced in (2 ·55') and (2 ·56).
§3. General formulation of the transfer matrix method

for chain molecules
Divide the chain molecule into N parts. We represent the displacements
of the atoms of part number j by the p;-dimensional vector u 1 Without

loss of generality we may take
(3·1)
In the normal vibration with angular frequency ro, these vectors satisfy
the simultaneous linear equations of the form
q
-ro 2 M1u 1 = ~ U 1 ,kUJ+k, (j= 1, 2, ... , N), (3·2)
k=-q
where M 1 and U1 ,k are matrices determined by atomic masse" and force

constants respectively, and q is the range of the force field.
By adding p- P1 auxiliary coordinates (p2p 1 ), we extend every u;
(j = 1, 2, • · ·, N- 1, N, N + 1, · .. , N + q) to a p-dimensional vector Cor res·
ponding to this we extend M1 and U;,k to p-dimensional matrices without
changing the relations between real original coordinates. We do thi:,; by
adding suitable matrix elements to M 1 and U 1 ,k in such a way that (i)
Det Uk,q=I=O, and (ii) the extended equation for u 1 insures the identity of
the p-p1 auxiliary coordinates of u 1 and those of UJ+q.*) In this way we
obtain the extended equations of (3 · 2).
If the extended equations coincide with the original. all auxiliary co·
ordinates vanish, and vice versa. Noting (ii), we find that the solution of
(3 · 2) is the solution of the extended equations which satisfies
(k= 1, 2, ... , q). (3-3)

Noting (i), we may introduce the transfer matrix of part j:
TJ==' - U].~U 1 ,q-1 -U].~U1 ,q-2 - Ui.~(U 1 ,o +ro 2 M 1 ) - UJ,~U;.-q

1 0 0 0
0 1 0 0
0 0 0 .1 0
(3·4)
*l For an illustration of the use of these auxiliary coordinates, see Example 5 in Append1x II.
34 H. Matsuda
Here 1 denotes a p-dimensional unit matrix. We have
(3·5)
where
UJ-1
(3·6)

UJ-q+l
UJ-1
(3. 6')
UJ-2o+1
1
and 0 ). (3·6")
0
Here 1 denotes a !-dimensional unit matrix, (l=pq).

Thus, as in §2 (liT!. we can rewrite the conditions (3 · 3):
A(w)w.=O, (3·7)
where
(3·8)
A.(w) is a !-dimensional matrix. The normal frequencies are to be deter-
mined by
DetA.(w)=O. (3·9)
We find that the simple linear chain considered in §2 is the special case
where p=q=l. Then the eigenvalue equation reduces to (2·25).
Just as in §2 when a majority of parts have the same M 1 and Up
(k= -q, -q+l, ···, q) and hence a common transfer matrix. we define a
basic part, a basic transfer matrix T, and a basic region. In the next section
we consider the general properties of the basic transfer matrix.
§4. Properties of the basic transfer matrix T

Consider the equation
(4·1)
From (3·4) and (3·6') we get
- '• (UJ,q-k+w 2 MJok,q)UJ-k+l

U1-;~ :b
k=l
(4·2)
Hence
(k= 1, 2, ... , 2q-1). (4·3)

Since in the basic region M 1 and UJ.k do not depend on j, we may
omit suffix j and write them as M and Uk respectively From (4·1), (4·2),
and ( 4 · 3) we find that the eigenvector v of T corresponding to the eigen-
value etA has a form:
=uX 1
v=[u
ue-"'
(4·4)
~e-tA(2q-1>
where u is the p-dimensional vector satisfying
1q
u= -Uq- 1 :b (Uq-k+w 2 Mok,q)e-w'u. (4·5)

k-1
Thus u and A can be determined as a function of w by the following

equatwns
Ru=O, (4·6)
DetR=O, (4·7)
where
R= :b• (Uk+w 2 Mok.o)em.. (4·8)

k=-Q
In this way the eigenvalue problem of the 2l-dimensional matrix Tis reduced
to that of the p-dimensional matrix R.
Now we study the symmetry property of Uk. Consider the harmonic
system with kinetic and potential energies of
and
respectively, where At denotes the transpose of the matrix A. This system

coincides with the system specified by (3 · 2) if we set
36 H. Matsuda
(4·9)
Hence
UJ.-k= ~ (VJ.-k+ V)-u). (4·10)
We may assume that when part j is in a basic region, V 1,k does not depend
on j. Therefore from ( 4 · 9) and ( 4 ·10) we obtain

From (4·11) and from the reality of the matrix Uk, we can state that:
If J..=qJ-i"/r (({J and "/r are real) satisfies (4·7), so do J..= -({J+i"/r and
± (fP+i"/r), too. Therefore, we label the 2l eigenvalues of the 2l-dimensional
matrix T as follows:
Aa.=(/Ja.-i"'ra., (a=-l, -l+l,···, -2, -1,1,2, ··,l), (4·12)
where f/Ja. and "'ra are real and satisfy
Aa.=-A-a., (4·13)
for a>{j, (4·14)
for and only for szaz-s'

(s=0,1,2, · ·,l), (4·15)
for sza>O. (4·16)
From (4·13), (4·14), and (4·15)
for a>s,
for a<-s. ( 4·13')
From ( 4 ·15) we see that there are 2s eigenvalues with real Aa.. We may
classify the frequency regions by the value of s. In the region where s=O,
no extended mode exists. And in the region where s=l, no damping mode
exists.
Let ro = roa. correspond to Aa. = 0. Then we obtain from ( 4 · 7), ( 4 · 8),
and (4·11) for Aa.=O
(4·17)
*> When UJ contains auxiliary coordinates, this relation does not necessarily hold. But the
basic transfer matrix T is reducible into the sub-matrix in the real and auxiliary coordinate
spaces, and since (4·11) holds in the real coordinate spaces, the presence of auxiliary coordinates
is not serious in the eigenvalue problem of T. Because of the condition (ii) of §3, the sub-
matrix in the auxiliary coordinate space is the unit matrix.
where
p
~ (Uk+ UO •• ~R~~,>
Ck = --"''·-=-•:,.::=_o_l_ _ _ _ _ __ (4·18)
~ M•• ,m~;
e, e' -1
m~; is a cofactor of DetL~. (Uk+ro~M8k,o) J.

Similarly when ro=wa corresponds to ..la=1t' we obtain for l..la-1t'l<1
(4·19)

where
(4·20)
ii~g) IS a cofactor of De{.~. ( -1)k(Uk+ w~M8k.O) J.

There is a one-to-one correspondence between the eigenvalues of T and
T'. If we introduce the row-vector v<al such that
(4·21)
then we have
when (4·22)
Therefore, when there is no degeneracy in the eigenvalues of T, *> the
transfer matrix T can be diagonalized as follows:
s- TS=A=
1 ev.., 0 0
0 ev..,_, 0
0 0 0 (4·23)
0 0 e-tA,
where
S= ( v<n v<z- 1> • • v<-z>)' (4·24)
s-1= vm
i)(!-1)
(4·24')
i)(-!)
*> In the following we consider only these cases. We hope this will make no serious
restriction of the applicability of our theory.
38 H. Matsuda
Since T Is a real matrix we note from (4·12)-(4·16) that when

sLaL-s,
(4·25)
where * denotes a complex conjugate. We also note that when a>s, there
exist vectors v<l3> anp v<l3l (fJ>s) such that
(4·26)
§5. End effects on the frequency spectra

In this section we generalize Example 3 in §2. Consider the model
specified by (2·50)-(2·51'), but now the transfer matrices are generally
2/-dimensional matrices, which are not necessarily 2-dimensional matrice" as
in §2. This case is physically of interest, for many chain molecules may
be well represented by this model.
Using (2·50)-(2·51'), (4·23)-(4·24') in (3·8) we obtain
I
A( co)= ~ ev.•N x<a>y<a.>' (5·1)
at--1
where
(5·2)
and
(5·2')
are /-dimensional column and row vectors.

From (5 ·1) we get
I
DetA(co)= :L; exp[iN:L; Aa.]/(a 1 , a 2 , .... at), (5·3)
Gt\1>tt2>···>~l n=]
where
/(ah a2, ... , at)=Det(x'"''x'"'''"·x'"''') Det y<" 1'
y<a,.
(5·4)
and the summation extends over all possible sets of a 1 , a 2, ... , ak, at,
(ak= -1, -l+ 1, '", -·1, 1, ... , l).
When N":;P-1, we can reduce the eigenvalue equation
DetA(co) =0
to:
Do(co) + D 1 (co) =0, (5·5)
s
Do(ro) = ~ g(a1 , a 2, ... , a,) cos [N~ q;>a. + o(a1, a2, ···,a,)],
'"'"''>"'•>···>... <:-• •-1
(5·6)
(5·7)
where
g(al> a2, '",a,)== lf(l, l-1, ... , s+1, a1, a2, ... , a,) I. (5·8)
a(al, a2, ... , a.)==argf(l, l-1, ... , s+1, al, a2, ... , a.). (5·8')

Here we have used the relation derived from ( 4 · 25) and ( 4 · 26) that
f*(l, l-1, '", s+l, a1, a2, ... , a.)=f(l, l-1, ... , s+1, -a., ... , -a1 ).
(5·9)
From (5·8) and (5·9) we obtain
(5·9')
(5·9")
When s=O,
Do(ro)=f(l, l-1, ... , 2, 1). (5·10)

If the frequency w satisfying D 0 (ro)=O is m the region with s=O, it cor-
responds to a damping localized normal mode. Whitcomb, Nielsen, and
Thomas10 ) called this type of vibration end vibration
When s=1, from (5·6), (5·9') and (5·9") we get
Do(w) =2g(l)cos [Nq;>1 + lJ(1)]. (5·11)

Therefore,
q;>1=nn/N+(; -a(l) )jN, (n: integer), (5·12)
gives an extended normal mode. This is just the extension of (2 ·56) for a
simple linear chain.
Snyder12> analysed his infrared data of n-paraffins assuming that the phase
is given by
q;>=nn/(N-1), (n= 1, 2, ... , N-1), (5·13)

where N is the number of carbon atoms.
Recently, Takase and the present author reanalysed his data and found
that the neglected term ( ; - a(1) )/ N makes a considerable contribution
in the methylene rocking-twisting modes. The analysis will be given in
40 H. Matsuda
Appendix I. Since <p1 and B(1) are independent of N. the formula (5 ·12)
may be used as an extrapolation and interpolation formula for the spectra
of homologous series.
If the frequency ro satisfying
g(1)=0 (5·14)
is in the region with s= 1, it corresponds to a localized mode. This can be

visualized as follows :
When part j is in a basic region we obtain from ( 3 · 5), ( 4 · 23)-

(4·24'), and (5·2')
I
= ~ et"-.Jv(a>_yca>wq . (5·15)
a~--1
By (5·14), (5·8), and (5·4) either
(5·16)
or
Det[ y'' =0.
y(l-1)
(5·16')
y-w
First we consider the latter case. From (5 ·16') we have a non-vanishing

W0 such that
(a= 1, 2, ···, l). (5·17)

By (5·16') any w. which satisfies a set of (l-1) equations
((1=2, 3, ···, l), (5·18)
also satisfies
(5·19)
On the other hand, because of ( 4 · 26) if w 0 satisfies (5 ·18) so doe~

Hence w. can be taken as real and from (4·25) and (5·19) we havt·
(5·20)
From (4·12), (5·15), (5·17), and (5·20) we obtain

-2
VJ+q= ~ eC'/IaH9'a>JvCa>y-ca>w0 • (5·21)
a;=-1
When the non-vanishing w 0 also satisfies

The Transfer Method in the Theory of NormaL Vibrations 41
(-l<a<-2), (5·20')
it corresponds to a localized mode but not a damping mode. Excepting such

exceptional cases, Eq. (5 · 21) represents a damping mode which is damped
with increasing j, because <tfr'a.<O by (4·13)
When (5 ·16) holds and (5 ·16') does not hold, similar arguments lead
to for j>1:
I
VJ+q= 2j e<'flaH9'alJv<a.ly<a.)Wq, (5·22)
al=-2

where Wq satisfies
I
2J e<'flaH9'alN x<a.ly<a.lwq=O. (5·22')
ao-•
Eq. (5 · 22) usually represents a damping mode which is damped with de-
creasing j.
These discussions suggest the possibility of the coexistence of extended
and damping modes in the frequency region where l>s= l. This is a new
bature which was absent in a simple linear chain where l = l. That this
is actually possible will be shown in Example 4.
When s=2, from (5·6), (5·9'). and (5·9") we get
(5·23)
where
g+=2g(2, 1), o+=o(2, 1). q:>+=q:>2+q:>1.
g-=2g(2, -1), iL=o(2, -1), q:'-=q:>2-q:>,,
go= g(2, - 2) + g(1, -1). (5·24)
When we remember that q:>+ and q:>- nre the functions of m and are not
independent of each other we may naturally ask: Does the approximate
eigenvalue equation
D 0 (m) =0. (5·25)

w:hich is valid for N>L have always a solution in any frequency interval
where s=2?
Consider the system with the same structure in the basic region bur
with a cyclic boundary condition The transfer matrices are given by
(j= 1, 2, ... , N) (5·26)

As m §2 (I) the frequency m is determined by
(5·27)
42 H. Matsuda
where 1 is a 2l-dimensional unit matrix. When s=2, from (4·23). (4·14).

and (4·15) we have
or (5·28)
where n 1 and n2 are integers.

Thus we have seen that by only modifying the N 1 + N 2 transfer matrices
and boundary conditions we always have a stationary normal mode at any
frequency interval where s= 2 if N is sufficiently large. Since N 1 + N2 1s

assumed independent of N, the question should be answered affirmative in the
limit N~=. because there is an important theorem proved by Ledermann: m
If in a Hermitian matrix the elements of r rows and their corresponding
columns are modified in any way whatever, provided only that the matrix
remains Hermitian, then the number of latent roots which lie in any given
interval cannot increase or decrease by more than 2r. As a consequence.
we must have the inequality:
g++g-2:go. (5·29)
When g+=g_ and go=O, Eq. (5·25) reduces to
cos( N({J2 + 8 +; 8- ) cos( Nrp 1 + 8 +; )=o.

8- (5·30)
Hence
(5·31)
or
(5·31')
Just as in (5·28) either ({J2 or qJ 1 is quantized.

In general we can solve (5 · 25) for ({J+ or ({J-:
(e= + or - ), (5·32)
where n is an integer.
When (5·33)
({J± is approximately quantized as
2; + ~ {11±-Cos-1( -g;:go )}<qJ± < 27; + ~ {o±-cos- g'f;,go )}.

1(
(5·34)
If (/)± defind in (5 · 24) is a monotonic function of q;'f in some frequency

range, from (5 · 32) and (5 • 33) every integer is allowed for n as long as it
gives the value of qJ± in the prescribed range. In Example 4 in Appendix
II, we shall show that (5·33) may actually be satisfied. When (5·33) does
not hold, although Eq. (5·32) is still valid, not every integer n may be

allowed even if the right-hand side of (5 · 32) gives the value for (/)± in the
prescribed range.
Without going into details for more complicated cases where s>3, we
conclude this section by stating: When the perfect translational symmetry
is assumed, one of the phases q;1 , q;2 , •• ·, ({Js is quantized as in (5 · 28), so that
the allowed phases are equally spaced. When the end effect is considered,
by (5 ·12) the equal spacing of allowed phases still approximately holds for
s=1 and N';Pl. But this no longer necessarily holds for s22.
§6. End effects on the intensity of the infrared absorJ?tion

Generally, the intensity of the infrared absorption due to the n-th normal
mode with displacements u 1 (n), (j= 1, 2, ... , N) is proportional to the square
of the induced dipole moment, which may be assumed as
N
p<al(n) = ~ Pj"luJ(n), (a=x, y, z). (6·1)
j-1
Here Pj"l is the 1 X p matrix which gives the a-component of the induced
dipole moment due to the displacement u 1 • The displacements u 1 (n) must
satisfy the normalization condition
N
~ u~(n) M 1u 1 (n)
j-1
=1. (6·2)
In order to study end effects we take up the model considered in §5.

Let us assume that in the basic region the consecutive r sites (r= 1, 2, · · ·)
form an optical unit cell such that
for j=mr+h, (6·3)
where m is an integer and h= 0, 1, 2, •· ·, r-1.

For s=O, the normal mode, if it exists, is an end vibration, so that the
intensity is almost independent of N.
For s21. there are extended modes. For these modes wq(n) given by
(3 · 6) must satisfy
44 H. Matsuda
1
A(w)wq(n) = ~ eiAaN x<aly<alw 0 (n) =0. (6·4)
dJ=-1
When N>1 and D 0 (w)=O, the equation

I
~ eiA•Nx<«ly<«>wq=O (6·5)
m=-s
has a non-vanishing solution w.. Remembering the labelling of Aa given in

§4, we note that usually lei/Jm_yca>w.l (/1=s+1, s+2, ···, l) must be of the
same order of magnitude as IY"lw. I, (a= -s, ···, s), in order to satisfy

(6·5).*l Therefore, IY 131 w.l, (8= -l, -l+1, ···, -s-1), must be of the
same order of magnitude as ly<" 1w.l, (a=-s, ···, s). Hence Wq in (6·5)
may be identified with w.(n) in (6·4).
In general the displacement uJ(j= 1, 2, ···, N) is a linear combination
of y'a.'?fJ., (a= -l, -l+1, ···, l), as given in (5·16). The above discussion
indicates that in the extended normal mode the contribution from j'131 w 0
(S>s or 8< -s) to u 1 can be at most of the same order of magnitude as
y'a'w• ( -s<a<s) only at or near the end parts. Therefore in evaluating
the left-hand side of (6·2), we may put
s
UJ(n) = ~ ei'P.<J-•>u<«>y<a>w.(n). (6·6)
c»=-s
Substituting (6·6) in (6·2) we obtain
2N~
. (uca>I-Mu<" 1 ) {w.(n)tjCa>t_ycalw.(n)}=1, (6·7)
m=l
where t denotes the Hermitian conjugate. Therefore if we put
then
(6·9)
*l Usually,
I"'A' eilaNx''<>y<«lwol/ "'}:;_' iyC«lwql =0(1),
I i:, eilpNx<fi;yCP!wql/1 ±
f3=s+l . r»=-s
eilaNx(«ly<«lwqi=O(l),
Here we have used the fact that usually no change in the order of magnitude occurs by taking
the linear combinations in the left-hand sides of the above equations. Because in order to produce
such a change, s or l-s variables yC«lwo must satis{y l simultaneous equations, since xC«l is a
!-dimensional vector. This is usually impossible.
From (6·6) we obtain
(6·10)
When
21t'
cpa=-m, (m=O, 1, ··· [r/2]), (6·11)
r
(6·10) may become very large. In such cases P(">(n) g1ven by (6·1) and

(6·3) may be approximated by
p<">(n)=- 1 ±-~Im[.P;,.o->(1-e;;N.<~9'~)u(a>y(a>]w9 (n), (6·12)

~ N "'-1 r£1cp"'
where
Am_ 21t'
,{.lcp"'=cpa---m,
r
(6·13)
r-1
p;,.o->:==b P).">eH27r/r)mlt. (6·14)
h-0
When s=1, from (5·12) we may put
(6·15)
where n (~N) is an integer. Especially for m=O
do=(+-11(1) )jN, (mod. ~ ). (6·16)
Substituting (6·15) in (6·12) we get
p<"l(n)=- 1
~N
(6·17)
where in the double sign the upper (lower) sign is for even (odd) n.
Therefore, the extended mode may be divided into two groups according as
n is even or odd. In other words, each neighboring mode belongs to a
different group.
In Eq. (6·5) for determining wq(n), the matrix (e;;9',N x(ilyW +e-i9',N
xH>yH>) is almost invariant when 'Pi changes by 2n"/N On the other
hand when ..la (/3=2, ... , l) changes corresponding to the change in 'Pi, the
I
change in b e;;~~N x(i3> j< 131 Wq can be compensated by a small change in w.,
13-2
46 H. Matsuda
smce a very small change in y( 131 Wq gives an appreciable change in the above
expression. Therefore Wq(n) is almost unaffected when n changes by 2.
Since the intensity is proportional to IP("1 (n) 1 2 , it has a peak at n=O.
By (6·17), in each group the intensity is approximately proportional to n-2 •
The intensity is O(N) for the peak since L1m=O(N- 1 ). The absorption at
the frequency separated from that of the peak by a finite amount has the
intensity of O(N-1).
When r= 1, the intensity has a peak only at <p1 =0. When r= 2, the
intensity has peaks at <p1 =0 and rc.

Remembering (4·17) and (5·12) when <p 1=0 the state density of the
normal vibration is proportional to {f)/ I (1) 2 - {f)~ 1 112 in one side of (1) 1 which
corresponds to the peak. On the other hand n is almost proportional to
I (1) 2 -{f)~ 1 112 • Therefore, the absorption intensity per unit frequency range is
proportional to I(1) 2 - {f)~ 1-312 in one side of the peak as Rosenstock 11J pointed
out for a simple linear chain. Similarly, by ( 4 · 19) it is proportional to
1(1) 2 - ro~ 1-312 in one side of the peak when (/>1 =rc.
When r~3, the intensity may have a peak or peaks in addition to
those at <p 1 =0 or n. For such a peak which is at w=wc, the state density
usually has no singularity and the absorption intensity per unit frequency
range around the peak is proportional to lw 2 -{fJ;I- 2 • The intensity is ap-
proximately symmetrical around the peak.
Some of the above results were already obtained by Theimer13 J in the
case of n-paraffins. We have pointed out that these properties persist to
hold under broader assumptions.
§7. Concluding remarks

We have found that the transfer matrix method is very useful when
the system has few basic regions. In such cases, even if the system is
complex there are some general features in the normal vibration characterized
by the s-value. Therefore, when s=O or 1, a simple linear chain can
represent the characteristic features of normal vibrations of complex systems
to a certain extent. But in general, unlike a simple linear chain, there may
be a damping normal mode in the frequency range where many extended
modes exist. This fact may have some bearing on the problem of the
existence of surface waves in the three-dimensional system.
As shown in Appendix I a phase shift analysis may be practical for the
extrapolation and interpolation of the normal frequencies of homologous
series. But the main purpose of the present article is rather in the elucida-
tion of mathematical aspects, so that we leave the detailed comparison with
experiments to a separate paper.
Acknowledgements
The author wishes to express his sincere gratitude to Prof. T. Yamamoto,
Prof. J. Hori, Mr. K. Okada, and Dr. H. A. Brodowsky for valuable sugges-
tions. He is grateful to Dr. R. G. Snyder for informing him of his experi-
mental results prior to the publication. He is also indebted to the mem-
bers of the Third Symposium on the Theory of Lattice Vibrations of
Imperfect Crystals held at the Hokkaido University in June 1962, for their
discussions.

Appendix I
Snyder et a1.12) gave a complete array of methylene rocking-twisting
modes for CaH8 through n-CaoHe2 as shown in Fig. 1. The assignment of
n integers introduced in (5 ·13) to bands in the spectrum amounts merely to
counting bands in the order of increasing frequency, remembering that only
bands corresponding to an odd n are infrared-active for reasons of symmetry.
1000 950 900 850 800 750 700

Frequency, em-'
Fig. 1.1 2 > Methylene rocking-twisting mode array for n-paraffins.
CaRs through n-Ca 0H,. (n values at left).
48 H. Matsuda
They also gave a plot of the wave number (J)/2rrc (c: the light velocity)
against ({J/rr given by (5 ·13) as shown in Fig. 2. Although points for the
longer molecules tend to converge to a common curve, points for the shorter
molecules tend to be displaced to high values of ({J/rr. These displacements
are considered to result from the interaction between methylene rocking
and methyl out-of-plane rocking, that is, the end effect.
cm- 1
1050
.....·i:

8
1000 •I • 6
•••• .11
950 .....
••:...
• I •S • •
.7
9
4
...... 10
900
••
.·.
0
.......
lo 8 •
850 5
.. .
_.. 9
800 ••• • "6
750
~o~-------no~.2--------,o~.4--------,o~.6~------,o~.8~-------~~.o~
91"
Fig. 2. Data points for selected n-paraffins indicated: 3=CaHs, etc.
The frequency range from 700 cm- 1 to 970 cm- 1 has no chain mode
besides the rocking-twisting modes, so that we may put s=1, and the phase
({J or ({J 1 must be given by (5 ·12) in our theory. From Fig. 1 we can assign
the value of N (not necessarily an integer) for each set of the frequency
and n-value. Using the value of N thus obtained, we plot in Fig. 3 the
value of n/(N-1) against 1/(N-1) at several frequencies. Every point
for the fixed frequency is almost on a straight line, showing that (5 ·12) is
correct.*>
The ex... apolation by the straight line to N~= in Fig. 3 gives a more
reliable frequency-phase diagram shown by the solid line in Fig. 2 than that
obtained by merely connecting points for longer molecules.
Thus we find that the scattered points for shorter molecules in Fig. 2
can be quantitatively accounted for by the phase shift ( ; -0'(1)) (N-1),
and that the molecules with N=30 are not necessarily long enough from
*> See page 58.
which to deduce the frequency-phase diagram by using Eq. (5 ·13) based on

the simplified model. The discrepancy amounts to about 13 cm- 1 for 0.7<
q>j1t'<0.85 in Fig. 2.
We hope the formula (5·12) is generally useful for assigning the in-
frared spectra of homologous series of chain molecules and obtaining the
frequency-phase diagram from them.
n
N-1
1.00
1037.5cm-1

0.92
0.90
0.88
0.84
0.82
0.80
0.52
0·50 0.02 0.04 0.06 0.08 0.10 0.20 0.30 1

N-1
Fig. 3.
Appendix II
Example 4. (the ladder model; p=2, q=1, free ends)
Set N pairs of atoms as in Fig. 4, and denote the one-dimensional
50 H. Mat~mla
displacements of the atoms by z1 and z;, (j= 1, 2, ···, N). Let K. K' and
K, (K~K'), be force constants. The atom at the N·th part the displace-
ment of which is denoted by
.z~ has the mass M'. All other
atoms have the mass M. The
equations of motion for fre-
quency ro are given by Fig. 4.

- Mro 2.z1 =KC.z2+ .zo- .z1) + K(.z~- .z1),
- Mro 2.z; = K' (.z~+ .z~- .zD + KC.z1- .z~),
- Mro 2.zN=K(tN+l + ZN-1-.zN) + K(.z~-.zN),

- M'ro 2.z~= K' (.z}, >1 + .z~-1- .z~) + K(.zN- ZN ), (ATT·l)
where M' = M(l + Q) and the auxiliary coordinates .z0 , .z~, ZN+h and z~+l
are introduced.
Parts j=2, 3, ... , N-1 form a basic region. In the basic region we
have
I -2K-K K ) 0 ).
Uo= (
U1=U-1=(K (AU ·2)
K -2K'-K ' 0 K'
In the end parts we have
( -K-K K )
(j=1, N).
UJ,o= K -K'-K '
(All ·3)
Therefore, the transfer matrix is given by
T1 =T= 2+(K-Mro2)/K -K!K -1 0

(j"=t=1, N)
-K/K' 2+ (K- Mro 2 )/K' 0 -1
1 0 0 0
0 1 0 0 (AU ·4)
Rt=Tt=T+ -1 0 0 0
0 -1 0 0
0 0 0 0
0 0 0 0 (AU ·5)
R2=TN=T+ -1 0 0 0
0 -l+A 0 0
0 0 0 0
0 0 0 0 (AII·5')
where A=-Qw2 /K'.

Substituting (AII·2) in (4·8), we obtain from (4·7) the relation between
the frequency w and the eigenvalue etA of T such that

Mw 2 =K + (K + K') (1-cos..l) ± Y (K- K') 2 (1-cos.<) 2 + K 2 • (AII·6)
This relation is schematically shown in Fig. 5.
IV (s=O)
I
--------- -L---
MOJ! I
I III (s=l)
I
I
--- --l- ---
MOJ'!.. I
I
I
I II (s=2)
I
I
I
_ _ _ ,.l _ _ _ _ --
1 2K I (s=l)
-1 0 cos ,l
Fig. 5.
Remembering §4, we have the following four frequency regions:
Region 1:
Region II:
2K/M<w2 <w'!={K+2(K+K')-Y4(K-K') 2 +K2 }/M, s=2;
Region III:
w'!<w 2 <w'1.= (K + 2(K + K') + Y 4(K- K') 2 + K 2} I M, s= 1;
Region IV:
According to the rule of labelling eigenvalues of T given in §4, we choose

the upper sign ( +) in the right-hand side of (AII·6) for .<=..!1, and the
lower sign (-) for .<=..!2 in Region II, III, and IV. In Region I the choice
must be reversed but we do not consider Region I in the following.
Using ( 4 · 4) and ( 4 · 6), we obtain eigenvectors of T:
52 H. Matsuda
c2r2
r2
c2r21
r;l
17 <1l = ( 1 ) X I ~~ )
c1 \ r1 , (All·8)
where

c1= [(K-K')(1-cos,h)-Y (K-K') 2(1-cosA 1) 2+K2]/.K, (All·9)
c2=K/ [ (K- K') (1-cosA 2) +,I (K- K') 2(1-cosA 2) 2+ K 2 ]. (All· 9')
Considering the orthonormality conditions ( 4 · 22), we also obtain the

left-hand side eigenvectors of T:
V121 =N2( -cl 1) X (r2 -r21 )=N2( -clr2 r2 clr21 -r;a1 ),
(AII·lO)
where
(a=1, 2). (All ·11)
Substituting (All·S), (All·5'), (AII·10) in (5·2) and (5·2'), we get
x 121 =r~( c2Cr2-r21) ) x 111 = r~( r1-r11 )

Cr2-r2 1 ) + Ar21 , cdCr1-r11) + Ar11} ,
(All·12)
Hence
Det(x 121 x 111 ) = (rt-r11) Cr2-r21) Cc1c2-1)
-A {r21(rt-r11) -c1c2r11Cr2-r21)}, (All·l4)
Det(x 121 x 1- 11 ) =- (r1-r11) Cr2-r21) Cc1c2-1)

+A {r21(rt-r11) +c1c2r11(r2-r21)}, (All·14')
(a=1, 2); (All ·14")

~(2)
Det( ~w ) =N1N2Cr1-r11) (r2-r21) Cc1c2-1), (AII·15)
(All ·15')
(a=1, 2). (All ·15")
Let us focus our attention on Region III where s= 1. In this region
cosA2< -1 <cos .h <1. (All ·16)
Substituting (All·14) and (AII·15) m (5·4), we obtain from (5·8):
g(1) =I N1N2Cr1-r1 1 )(r2-r~ 1 ) Cc1c2-1) I

x I Cr1-r11) Cr2-r21) Cc1c2-1)- A {r21(rl-r1 1) -c1c2r11(r2-r21)} 1.

(All·17)
As mentioned in §5 we want to show that in some cases it can actually

happen that the frequency (J) which satisfies (5 ·14) is in this range. First
we note from (All·8)-(All·9'), (AII·ll), and (AII·16) that: if A=O,
then
g(1)=FO . (All ·18)
For simplicity we consider the case in which
K~K-K'. (All ·19)
Then we have from (All·6), (All·9), and (All·9'):
M(J) 2 =K + 2K(1-cosA1) +O(K2)

= K + 2K' (1-cosA2) + O(K2), (AII·20)
K -
c1 = - 2(K-K')(1-cosA 1) +O(Ka), (AII·21)
K - (All·21')
c2= 2(K-K')(1-cosA 2) +O(Ka).
Neglecting the terms of O(K2), we get
g(1)= I (1+Q)t2- {1+Q(2+K/K')}t+QI, (AII·22)

where t=r§. By (All ·16)
t<-1. (AII·23)
From g(1) = 0, we obtain noting (All· 23)
t= Q-(l+Q)K/K' +O(K2) (AII·24)

1+Q .
Because of (AII·23), (All·24) and (AII·19),

54 H. Matsuda
Q< -1+K/K' (AU ·25)

2-K/K'
When K=O, (AII·25) is equivalent to (2·49) with h=1 and N';;P1, as it

should be.
From (Ail· 20) and (All· 24) we have
Mw 2 =K+2K'[ 1- Q;~s:8{ ++{1-( 1 ~9_ rt ~, ].

(All ·26)
Since the frequency must be in Region III we have
K'[1- Q2+(1+Q)2 +-1 {1-( 1+Q

2Q(1+Q) 2 Q
)2} K-]<zK
K' = .
(Ali ·27)
Thus we find that when (All ·19), (All· 25), and (All· 27) are all satisfied,
which is made possible by setting K and Q sufficiently small and K suffi-
ciently large, Eq. (5·14) is satisfied in Region III, so that the reg'o:J w1th
s= 1 may have a damping normal mode.
Next we consider Region II. Substituting (All ·14)- (All ·15") in (5 · 4)
we obtain from (5 · 8) and (5 · 24)
go=O,
g+fg-=1 Cr1-r11) Cr2-r21) (c1c2-1)- A {r21Cr1-r11) -c1c2r! 1(r2-J'i 1)} ,.
(r1-r 11) Cr2-r21) (c1c2-1)- A {r2 1Cr1-r11) + c1c2T!1Cr2-r2 1 )}
(All·28)
Therefore when Q:t=O, the inequality (5·33) is actually satisfied.
Example 5.
Kr>
Consider the one-dimensional
system of (N+2) atoms shown in
Fig. 6. Let the displacements z!, [(!
!, -- __,z;>-._!.:.::K_z..,i_K_...zi+-1 --
z.v
zt, and z 1 , (j= 1, 2, ···, N), satisfy Zt

Fig. 6.
the following set of equations
j -M'w2z;-=K'(z1-z]) +K'z2,
-M'w 2zi=K'(zt-zi)+K'zi,
- Mw 2z1 =K'(zi+z;--2z1) + KCz2-z1),
J- Mw z 2 1= K(z 1 +1 + ZJ-1- 2zJ), (AII·29)
\ (j=2, 3, N-1),
r- Mro zN= K(zN-1- ZN) + KzN+1.

2
\ z~=z~+1,
Here ZN+l and zj, (j=2, 3, ... , N, N+1), are auxiliary coordinates.
According to the general prescription given in §3, we define a set of
3-dimensional vectors :
u1 =( z1 ) ,
(j=1, 2, ···, N, N+1).

zj
Zj
Then p=3, and q=1; and
R1.E'=T1F= 1 + (2K'- Mro 2 ) / K -K~/K -K'/K

-1 1-M'ro2/K' 0
-1 0 1-M'ro2 /K'
1 0 0
0 1 0
0 0 1
(AII·30)
T 1 =T= 2-Mro /K 2 0 0 -1 0 0
0 1 0 0 0 0
0 0 1 0 0 0
1 0 0 0 0 0
0 1 0 0 0 0
0 0 1 0 0 0
F'R,~F'TN~[ 1-~w'/K 0 0 -1 0
1
0
0
1
The eigenvalues e'>..", (a= ±1, ±2, ±3), of T are given by, (see
0
0
0
0 H
Example 1 in §2) :
A±s = ±Cos-1 (1- Mro 2 / (2K) ),

.la=O for {j= ± 1, ±2,
v<a)= 1 1 x[ ra
),
¥r~-r;;: 2
[ 0
0
r;;:1
56 H. Matsuda
1)<etl= 1
vr~-ra 2
(1 0 0) X(ra r;:; 1 ), (All ·31)
where a=±3, ra=e"'al2;
•'"~[ X( ··-"~[
1 0
0
1 0 ), 0
1 r( )' 1
0 0
•'"~[ ··-"~[ ),
1 0
0
), 0
rr rr

0 0 0 1
1 1
v<Bl=v<B>• for S= ±1, ±2. (All ·32)
The vectors x<a> and y<a> which are defined in (5 · 2) and (5 · 2') are
given by
(a= ±3);
x<2>= 0
1
0
l, •'"~ l, 0
0
1
x<-11= 0
0
0
.·~·~[ 0
0
0
y<2l=( -1 1-M'w2/K' 0),
y(ll= (-1 0 1-M'w2/K'),
yH>=(O 0 1),
y<-21= (0 1 0). (All·33)
Substituting (All· 33) in (5 · 4) we obtain from (5 · 3) :
(All ·34)
When w<2vK/M, s=3. Equation (AII·34) indicates, however, that the

eigenvalue equation takes the same form as in the case discussed in §5 for
s=l. Similarly, when w>2vK/M, s=2. But the situation is just the
same as when s=O in §5.
This result indicates that when the basic region contains auxiliary co-
ordinates the characteristic features of normal vibrations can be determined
by the s-value defined by omitting the auxiliary coordinates. Namely, the
number of eigenvalues with absolute value 1 of the basic transfer matrix in
the sub-space of the real coordinates determines the essential features of
normal vibrations in the corresponding frequency range.
When ro=vK'/M', there is a normal mode such that
zi= -z1

(j=2, 3, ... , N). (All ·35)
This is a localized mode but not a damping mode defined in §2 and discussed
in §5.
References
1) E. W. Montroll and R. B. Potts, Phys. Rev. 100 (1955), 525; 102 (1956), 12.
2) E. W. Montroll, J. Chern. Phys. 10 (1942), 218.
A. A. Maradudin, P. Mazur, E. W. Montroll and G. H. Weiss, Rev. Mod. Phys. 30
(1958), 175.
C. Domb, A. A. Maradudin, E. W. Montroll and G. H. Weiss, ]. Phys. Chern. Solids 8
(1959), 419.
3) F. ]. Dyson, Phys. Rev. 92 (1953), 1331.
R. Bellman, Phys. Rev. 101 (1956), 19.
4) H. Schmidt, Phys. Rev. 105 (1957), 425.
5) P. Dean, Proc. Phys. Soc. 73 (1959), 413; Proc. Roy. Soc. A 254 (1960), 507.
P. Dean and ]. L. Martin, Proc. Roy. Soc. 259 (1960), 409.
]. L. Martin, Proc. Roy. Soc. 260 (1961), 139.
6) ]. Hori and T. Asahi, Prog. Theor. Phys. 17 (1957), 523.
J. Hori, Prog. Theor. Phys. 18 (1957), 367; 23 (1960), 475.
7) ]. S. Faulkner and J. Korringa, Phys. Rev. 122 (1961), 390.
8) For example, see the review articles:
]. Lecomte, Handbuch der Physik (Springer-Verlag, Berlin, 1958) Vol. 26, p. 244.
L. J. Bellamy, The Infrared Spectra of Complex Molecules (Methuen, London, 1958).
9) ]. G. Kirkwood, ]. Chern. Phys. 7 (1939), 506.
K. S. Pitzer, ]. Chern. Phys. 8 (1940), 711.
T. Simanouchi, J. Chern. Phys. 17 (1948), 734, 848.
T. Simanouchi and S. Mizushima, ]. Chern. Phys. 17 (1949), 1102.
H. Primas and H. H. Giinthard, Helv. Chim. Acta 36 (1953), 1659, 1791.
M. C. Tobin, ]. Chern. Phys. 23 (1954), 891.
C. Y. Liang, S. Krimm and G. B. B. M. Sutherland, }. Chern. Phys. 25 (1956), 543.
S. Krimm, C. Y. Liang and G. B. B. M. Sutherland, J. Chern. Phys. 25 (1956), 549.
P. Higgs, Proc. Roy. Soc. 220 (1953), 472.
T. Miyazawa, J. Chern. Phys. 35 (1961), 693.
10) S. E. Whitcomb, H. H. Nielsen and L. H. Thomas, ]. Chern. Phys. 8 (1940), 143.
11) H. B. Rosenstock, ]. Chern. Phys. 23 (1955), 2415; 27 (1957), 1194.
12) R. G. Snyder, J. Mol. Spectroscopy, 4 (1960), 411; 7 (1961), 116.
R. G. Snyder and ]. H. Schachtschneider, Spectrochim. Acta.
]. H. Schachtschneider and R. G. Snyder, Spectrochim. Acta.
13) 0. Theimer, ]. Chern. Phys. 27 (1957), 408, 1041.
58 IL Matsuda
14) T. Yamamoto, H. Matsuda and K. Okada, Preprints oj the 1962 International Symposium
on Molecular Structure and Spectroscopy at Tokyo, C202.
15) J. Hori, Prog. Theor. Phys. Suppl. No. 23 (1962), 3, this issue.
16) P. W. Anderson, Phys. Rev. 109 (1958), 1492.
H. Matsuda, Prog. Theor. Phys. 27 (1962), 81L
17) W. Ledermann, Proc. Roy. Soc. 182 (1944), 362.
*> The small deviation from the straight line may be attributed to the inter-molecular inter-
action in the crystal. For the frequency range above 970cm-1 there exists a C-C stretching
mode. The good fit of the formula (5·12) even for 1000, 1037.5, and 1050cm-• in Fig. 3 may
be due to the fact that the coupling with this mode is smalL

The Transfer Matrix Method in The Theory of Normal Vibrations of Chain Molecules

Caricato da

Informazioni sul documento

Titolo originale

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

The Transfer Matrix Method in The Theory of Normal Vibrations of Chain Molecules

Caricato da

Copyright:

Formati disponibili

Supplement ot the Progress of Theoretical Physics, No.

The Transfer Matrix Method in the Theory of

Department of Chemistry, Kyoto University, Kyoto

Downloaded from http://ptps.oxfordjournals.org/ at Pennsylvania State University on May 12, 2016

Downloaded from http://ptps.oxfordjournals.org/ at Pennsylvania State University on May 12, 2016

In §2 the transfer matrix method for a simple linear chain will be

Downloaded from http://ptps.oxfordjournals.org/ at Pennsylvania State University on May 12, 2016

§2. The transfer matrix method for a simple linear chain

mi1J=kJ(um-uJ) +kJ-1(UJ-1-uJ), (j=1, 2, ···, N). (2·1)

We call such a system a simple linear chain.

We call T 1 the transfer matrix of part number j. T 1 is determined by the

Downloaded from http://ptps.oxfordjournals.org/ at Pennsylvania State University on May 12, 2016

Hence we may define TN and T1 by (2·6) and we have

Det[HN-1] =0, (2·10)

where 1 is a unit matrix. Since

Trace HN=2. (2·11)

This is the eigenvalue equation for the frequency ro.

(II) Fixed ends

uo=uN+l =0. (2·12)

If we define the matrices

we obtain from (2 ·12) and (2 ·13)

UN+1 =A(m)ul =0, (2·15)

Downloaded from http://ptps.oxfordjournals.org/ at Pennsylvania State University on May 12, 2016

(III) Free ends

In order to define TN even in this case we introduce the auxiliary coordi-

UN+! =0, (2·19')

where k~ is an arbitrary non-zero constant Obviously the simultaneous

Using the transfer matrices defined in (2 · 6) for J = 1, 2, · · ·, N- 1, and TN

smce k0 =0. But we may as well write

where a is an arbitrary constant, since T 1F does not depend on the value

which leads to the eigenvalue equation

Downloaded from http://ptps.oxfordjournals.org/ at Pennsylvania State University on May 12, 2016

m 1 =M, k 1 =K, (}=1, 2, ···, N).

Then from (2·6), (2·21), and (2·23') we may put

~ 1 ), (}=2, 3, ···, N-1), (2·27)

w2 = (4K/ M)sin 2 (A/2) = (2K/ M)(l-cosA)_ (2·28)

r -~-1 ) • (2· 31')

Downloaded from http://ptps.oxfordjournals.org/ at Pennsylvania State University on May 12, 2016

A(ro) =2i r-r-: sin(NA.) . (2·33)

A.=mr:/N (n=O, 1, 2, ···, N-1). (2·34)

Thus we obtain the whole set of eigenfrequencies

ro=2VK/M sin(mr:/2N). (n=O, l, 2, ... , N-1). (2·34')

Generally, different part~ may have different transfer matrices But

From (2·5) and (2·30)

When A. is real, (2·36) represents an extended wave for a displacement

Downloaded from http://ptps.oxfordjournals.org/ at Pennsylvania State University on May 12, 2016

Without loss of generality we may take

tan( N- ~ )A=- (2Q+ l)tan(A/2) . (2·40)

~~ there exist N real roots for A in the region 0 <A<

Therefore, no damping normal mode exists if Q ~- + .

~ it can easily be shown that there exif'i N -1 rf'~ 1 roots

Then Eq. (2·40) becomes

Downloaded from http://ptps.oxfordjournals.org/ at Pennsylvania State University on May 12, 2016

n:(N-1)/(N-+ )<;.<n:. If (2Q-t 1)( N-+ ) < - + , Eq. (2·42) has

l=i'o/' or ).=n:-i'o/', ('o/': real),

m=2-.IK/M cosh('o/'/2)>2vK/M . (2·43)

Thus we have a damping norma. mode. H N';;P1, then from (2·42)

When h=/=1, we have

From A(m) =0, we obtain

-2Qtan()./2) = sin N).

=tan(N-h+ ; )).+tan(h- ; );. . (2·46)

If Q~O, Eq. (2·46) has N real roots in the region o<;.<n:.

2(N_!-h)+1 }. Using (2·41) we rewrite Eq. (2·46):