372 APPUCATIONS OF STATISTICS TO GASES 12-6
quantized character of these energies, which can take on only certain discrete
values and cannot be expressed as a continuous function of some coordinate. The
energy associated with them is not a simple linear function of the temperature.
12-41 THE QUANTIZED LINEAR OSCILLATOR
We consider next an assembly of N identical linear oscillators, assumed distin-
guishable so that we can use Maxwell-Boltzmann statistics. The properties of such
an assembly form the basis of the theo ry of the specific heat capacity of polyatomic
gases and of solids.
A linear oscillator is a particle constrained to move along a straight line and
acted on by a restoring force F - Kx, proportional to its displacement x fro m
some fixed p oint and oppositely directed. The equation of motion of the particle is
d'x
F = m dt' -Kx,
where m is the mass of the particle. If displaced from its equilibrium position and
released, the particle oscillates with simple harmonic motion of frequ ency •· given
by
., =.!. JK[;,.
2,.
The frequency depends only o n K and m, and is independent of the amplitude x,..
The energy • of the oscillator is the sum o f its kinetic energy mv'f2 and its
potential energy Kx'/2. Since the total energy is constant, and the kinetic energy
is zero when the displacement has its maximum value x,., the potential energy at
this displacement is equal to the total energy • and hence
,.! Kx!..
2
Thus the total energy is proportional to the squau of the amplitude, x,..
If the oscillators were independent, there could be no interchange
of energy bftween them, and any given microstate of t he assembly would continue
indefinitely. We therefore assume that the interactions between the particles are
large enough so that there can be sufficient exchanges of energy fo r the assembly
to assome all possible microstates consistent with a given total energy, but small
enough so that each particle can oscillate nearly independently of the others.
In classical mechanics, a pa rticle can oscillate with any amplitude and energy.
The principles of quantum mechanics, however, restrict t he energy to some one
of the set of values
(12-43)
!-6 THE QUANTIZED LINEAR OSCILLATOR 373
=
•here n1 0, I, 2, ... , and h is Planck's constant. An unexpected result is that
1e oscillator can never be in a state of zero energy, but that in the lowest level the
nergy ish•f2, in the next level it is Jh•/2, and so on. The levels are nondegenerate ;
:>ere is only one energy state in each level; and g1 - I in each level.
The quantum condition that the entrgy can have only some one of the set of
a lues [(n1+ l /2)h•J is equivalent to the condition that the amplitudt can have only
orne one of the set of values such that
x:O = (n1 + ; JI/Km.
U sing Eq. (12-43), the partition function of the assembly is
Z- !exp (-•
I kT
1
) - ! exp
I
[-(n + !) .!!!..].
1
kT2
n
fo evaluate the sum, let z - h•/kT for brevity. Writing out the first few terms,
ve have
z exp ( - + exp ( - ¥) + exp ( - ¥) + ...
- exp ( - n{l + exp ( -z) + [exp ( -z)J' + .. ·}.
rhe sum in the preceding equation has the form of the infinite geometric series
I+ P + p' + .. ·,
.vhich equals 1/ (1 - p) as is readily verified by expanding the product ( I - p ) X
(I + p + p' + · · ·). Therefore
Z exp ( - !)
1
2 I - exp ( -z)'
or
Z = exp ( -h•/2kT)
(12-44)
I - exp ( -h•/kT)
The temperature at which kT- /., is called the characteristic temperature of
the assembly and is represented by 0. Thus
kO = ho, or 0=!!!. (12-45)
k
It follows that
,. 0
kT
and in terms of 0 the partition function is
z= e xp ( -0/2T)
(12-46)
I - exp (-Of T)
374 APPLICATIONS OF STATISTICS TO GASES 12-6
The value of the partition function at any temperature therefore depends, fo r
a given assem bly, o n the ratio of the actual temperature T to the characteristic
temperature 6, which thus provides a reference temperature for the assembly.
The greater t he natural frequency • of the oscillarors, the higher the characreristic
temperature. Thus if the natural freq uency is of the order of frequencies in the
infrared region of the electromagnetic spectrum, say 10,. Hz, • then
O ,. !!! = 6.62 X 1()"',. J s X IO'' s-• == SOO K.
k J.38 x 10-" J K- '
An actual tempe ratu re T of SO K is then approximately equal to 6/ 10, and a
tempera ture of 5000 K is approximately equal to 10 0.
T he average fractional n umber of oscillators in the jth energy level, from Eqs.
( 12-16) and (12-43) is
n
IV 1I ( <1 ) l
( (n, + l)l••)
2
N - Z exp - k r •zexp - kT ·
Subsrituting Eq. (12-46) fo r Z a nd Eq. (12-45) for 0,
[r- exp ( Jexp ( - n 1 ) · ( 12-47)
At any temperature T, the occupation number decreases exponentially with the
q uantum number n1, and decreases more rapid ly, the lower the rem peratu re.
At the temperature at which T • 8,
(8/n• l,
and
!(
7:/ 0.632 exp ( -n1).
Thus for the four lowest energy levels, in which "J - 0, I, 2, and 3, we have
Flo R, Fl, R,
li- o.632, li - o.m, li - [Link]. li - [Link].
Abour 63% of the oscillarors are in the lowest e nergy level, abour 23% in the next Tl
level, ere. Togerher, rhe four lowest levels aecounr for about 98% of the oscillators. ter
It is left to the reader to show tha t when T • 0/2,
Ro R, Fl, lil,
li - o.86s. li - 0.111, li - o.o16, li = o.oo2.
• Heinrich R. Hertz, German physicist (1857-1 894).
12-6 THE QUANTIZED LINEAR OSCI LLATOR 3711
Atrhis temperarure, abour87" of the oscillaton are in the lowest level, about 12"
in rhe nexrlevel, ere. and almost allrhe parricles are in the firsr four levels.
At a remperature T - 28,
n. -
N 0.394,
n, -
N 0.239,
ll.
N - o.I4S,
n, -
N o.o88.
The first fou r levels then accounr for only about 86% of the oscillaron, the remainder
being disrribured among rhe higher energy levels.
The lengrhs or the verrical lines in Fig. 12-14 represenr rhe average fractional
occuparion numbers ar rhe remperarures T - 8/2, T - 8, and T - 28.
1.0
0.8
lllli
fl, 06
N
0.4
0.2
"J • 0 I l .1 0 I 2 J 0 t 2 l
T• T•D T• 20
Fig. 12- 14 The dependence on 8/T of the average
fracrional occuparion number of the first four ltvels
of a linear oscillator.
The total energy of the assembly, which in this case is its internal energy U, is
U- NkT'dln z
dT
- Nk8[ I
exp (8/T) - I
n.
+ iJ (12-48)
Thus for a given assembly of linear oscillators the internal energy is a function of
temperature only. The heat capaciry Cy of the assembly is
Cy = dU
dT
8)' exp (8fT)
- Nk ( - (12-49)
T (exp (8fT) - 1]2 •
378 APPLICATIONS OF STATISTICS TO GASES 12-7
Fia. 12-15 The internal energy
and heat capacity of an assembly
of linear oscillato11.
T he c urves in Fig. 12-1 S are graphs of the inter nal energy U and of the heat
capacity Cv (both divided by Nk) as functio ns of TfO. The ordinate of the latter
is proportional to the slope of the former.
As T approaches 0 K, very nea rly a ll of the oscillators are in their lowest energy
level with energy h•/2 and the total energy U approaches the zeropoint energy
Nh•/2, or, U/Nk - O.S. T he internal energy changes only slightly with changing
temperature and the heat capacity approaches zero. T he entropy of an assembly
of linearJscillators also approaches zero as T approaches zero.
Whe T » 0, 0/T« I, exp (0/T)- I 0/ T, the term 1/2 is negligible com·
pared with T/0, and U approaches NkT. The mean energy per particle, U/N,
approaches kT which is the val ue predicted by equipartitio n fo r an oscillator with
t wo degrees of freedom (its position and its velocity). The internal energy increases
nearly linearly with temperature and Cv approaches the constant val ue Nk.
12-7 SPECI FI C H EA T CAPA CITY O F A DIATO MIC GA S
I t was shown in Sectio n 12- 1 how the equation of state of a monatomic ideal gas,
and its energy equation, could be derived by the methods of statistical thermo-
dynamics. Consider next a gas whose molecules are polyaromic. If the energy
of a molecule does not depend on the space coordinates x, y, and z of its center of
mass, and if there is no mutual potential energy between molecules, the partition
function will be directly proportiona l to the volume V, as in Eq. (12-6) for a
monatomic gas. The Helmholtz function F = -NkT(In Z- InN+ I) then
has the same dependence on Vas for a monatomic gas and the gas has the same
of state, P V - nRT.
