A Polymer Model—The Rubber Band Revisited 339

temperatures, peakingin the region of ky7 = .42¢. This behavior is known

as a “Schottky hump.” Such a maximum, when observed in empirical
duta, is taken as an indication of a pair of low lying energy states, with all
other energy states lying at considerably higher energies. This is an
example of the way in which thermal properties can reveal information
aboutthe atomic structure of materials.

PROBLEMS

15.3-1. In the two-state model system of this section suppose the excited state
energy € of an “atom” depends on its average distance from its neighboring
atomsso that
a

|<
ce
e= y?

i
Qe

where a and y are positive constants. This assumption, applied to a somewhat

more sophisticated model of a solid, was introduced by Gruneisen, and y is the
“Gruneisen parameter.” Calculate the pressure P as a function of 6 and T.

Answer:
— price
P= 4 a/kgTo"
ee” + 1) -1

15-4 A POLYMER MODEL—THE RUBBER BAND REVISITED

There exists another model of appealing simplicity that is euphemisti-

cally referred to as a “polymer model.” Its connection with a real polymer
is tenuous, but that connection is perhaps close enough to serve the
pedagogical purpose of providing some sense of physical reality while
again illustrating the basic algorithm of statistical mechanics. And in
particular the model provides an insight to the behavior of a “rubber
band,” as discussed on purely phenomenological grounds in Section 3.7.
As we saw in that section the extensive parameter of interest, which
replaces the volume,is the /ength; the corresponding intensive parameter,
analogous to the pressure, is the tension. We are interested in the equation
of state relating tension to length and temperature.
The “rubber band” can be visualized as a bundle of long chain
polymers. Each polymer chain is considered to be composed of N mono-
mer units each of length a, and we focus our attention on one particular
polymer chain in the bundle. One end of the polymer chain is fixed at a
point that is taken as the origin of coordinates. The other end of the chain
is subject to an externally applied tension 7, parallel to the positive
X-axis (Fig. 15.4).
340 Statisncal Mechanics in Entropy Representation

String

[Frey
Z4 y
4 L,

Weight (=7)
FIGURE154
“Polymer” model. The string should be much longer than shown, so that the end of the
polymerts free to move in the y-direction, and the applied tension 7 is directed along the
x-direction.

In the polymer model each monomerunit of the chain is permitted to

lie either parallel or antiparallel to the x-axis, and zero energy is associ-
ated with these two orientations. Each monomer unit has the additional
possibility of lying perpendicular to the x-axis, in the +y or —y direc-
tions only. Such a “perpendicular” monomer unit presumably suffers
interference with other polymer chains in the bundle; we represent this
interference by assigning a positive energy e to such a perpendicular
monomer.
A somewhat more reasonable model of the polymer might permit the
perpendicular monomersto lie along the +z directions as well as along
the +y directions, and, more importantly, would account for the inter-
ference of a chain doubling back on itself. Such models complicate the
analysis without adding to the pedagogic clarity or qualitative content of
the result.
We calculate the entropy S of one polymer chain as a function of the
energy U = U’e, of the coordinates L, and L, of the end of the polymer
chain, and of the number N of monomer units in the chain.
Let N,” and N, be the numbers of monomers along the +x and ~x
directions respectively, and similarly for Ny" and N, . Then

Nv +N, +N +N, =N

_ OL
NN ==a
Ly

L
Ni -N, = =L, a .

N; +N os U" (15.14)
 A Polymer Model— The Rubber Band Revisited 34]

from which wefind

N, =3(U’- Li) (15.15)

The number of configurations of the polymer consistent with given
coordinates L, and L, of its terminus, and with given energy U,is

~ N!
2(U, Le Ly S) = SNE (15.16)

The entropyis, then, using the Stirling approximation (equation 15.3)

S = k,inQ = Nk,InN — Nik,InN* — Nok,In No

—N,k,ln NY — No kyIn Ny (15.17)

or

S = Nk,InN — 4(N — U' + L)kgln[3(N — U' + 1’)

—3(N — U'— Li)kpln[3(W — U' - L)I

—4(U' + L)kgin[3}(U" + L4)]
—4(U' — L)kyln[3(U" — 14)] (15.18)
With the statistical mechanical phase of the calculation completed, the
thermodynamic formalism comes into play. The y-component of the
tension YF, is conjugate to the extensive coordinate L, (see Problem
15.4-1). Setting TF, = 0 gives

vy
7v 3L, — By,
v4op7 (15.19)

from which we conclude(as expected) that

L,=L,=0 (15.20)
342 Stansucal Mechanics in Entropy Representation

Similarly

FZ, dS ky, N-U-L,

T 7 3L.* Ja" HD U tL (15.21)

and

7 50 = 7e nNA) + Li-U')+
1 — as — kp ’ ,
se in( NNY
ky
Li, U’'), Inv
ky ,

(15.22)

or
N _ pry? _ ye2
erestat — UY
(N= US ue
(15.23)

This is the “thermal equation of state.’ The “mechanical equation of

state” (15.21) can be written in an analogous exponential form

e -25,a/kgT N-U-WL. (15.24)

N-U+UL,

The two preceding equations are the equations of state in the entropy
representation, and accordingly they involve the energy U’. That is not
generally convenient. We proceed, then, to eliminate U’ between the two
equations. With some algebra we find (see Problem 15.4-2) that

Ly inh(.F T
Es, __sinh(Z.a/kT) (15.25)
N cosh(.Za/k,T) + e7 */*8?

For small Za (relative to k,7) the equation can be expanded to first

order

Le F.Na? 1
x k pT T+ ev tks? +++ (15.26)

The modulus of elasticity of the rubber band (the analogue of the

compressibility —1/V(dV/dP)-,) is, for small Z

1 {OL a?
ral aF. } = ie,‘ P+ e “ary!
Sloe] ( 15.27)
 Countng Techniques and their Circumvention, High Dimenstonality 343

The fact that this elastic modulus decreases with increasing temperature
(or that the “stiffness” increases) is in dramatic contrast to the behavior of
a spring or of a stretched wire. The behavior of the polymer is sometimes
compared to the behavior of a snake; if we grasp a snake by the head and
tail and attemptto stretch it straight the resistance is attributable to the
writhing activity of the snake. The snake, in its writhing, assumesall
possible configurations, and more configurations are accessible if the two
ends are not greatly distant from each other. At low temperatures the
rubber bandis like a torpid snake. At high temperatures the number of
configurations available, and the rate of transitions among them, is
greater, resulting in a greater contractive tension. It is the entropy of the
snake and of the rubber band that is responsible for the tendency of the
ends to draw together!
The behavior described is qualitatively similar to that of the simple
phenomenological model of Section 3.7. But compared to a truly realistic
model of a rubber band, both models are extremely naive.

PROBLEMS

15.4-1. Is the sign correct in equation 15.19? Explain.

15.4-2. Eliminate U/e between equations 15.23 and 15.24 and show that the
formal solution is equation 15.25 with a + sign before the second term in the
denominator. Consider the qualitative dependence of L,/Na on e, and show that
physical reasoning rejects the negative sign in the denominator, thus validating
equation 15.25.
15.4-3. A rubber band consisting of m polymer chains 1s stretched from zero
length to its full extension (L = Na) at constant temperature 7. Does the energy
of the system increase or decrease? Calculate the work done on the system and the
heat transfer to the system.
15.4-4. Calculate the heat capacity at constant length for a “rubber band”
consisting of n polymer chains. Express the answer in terms of 7 and L,.
15.4-5. Calculate the “coefficient of longitudinal thermal! expansion” defined by
,. 1/(4L,
“r= | oT \e
Express «7 as a function of T and sketch the qualitative behavior. Comparethis
with the behavior of a metallic wire and discuss theresult.

15-5 COUNTING TECHNIQUES AND THEIR

CIRCUMVENTION; HIGH DIMENSIONALITY

To repeat, the basic algorithm of statistical mechanics consists of

counting the numberofstates consistent with the constraints imposed; the