Chapter 8- Answers to selected exercises

1. Obtain the explicit forms of the ground state and of the rst excited state
for a system of two free bosons, with zero spin, conned to a one-dimensional
region of length 1. Repeat this problem for two fermions of spin 1,2.
*** The single-particle states are given by ,(r) = sin(/r), where / =
_
2:1,/ and /1 = :, with : = 1, 2, 8.... Note that ,(r) vanishes at r = 0
and r = 1.
The ground state is given by C sin(r
1
,1) sin(r
2
,1), where C is a nor-
malization constant.
The rst excited state is given by
1[sin(r
1
,1) sin(2r
2
,1) sin(2r
1
,1) sin(r
2
,1)[ .
2. Show that the entropy of an ideal quantum gas may be written as
o = /
B

j
)
j
ln)
j
(1 ()
j
) ln(1 ()
j
) ,
where the upper (lower) sign refers to fermions (bosons), and
)
j
= :
j
=
1
oxp[, (c
j
j)[ 1
is the FermiDirac (BoseEinstein) distribution. Show that we can still use
these equations to obtain the usual results for the classical ideal gas.
3. Show that the equation of state
j\ =
2
8
l
holds for both free bosons and fermions (and also in the classical case). Show
that an ideal ultrarelativistic gas, given by the energy spectrum c = c//, still
obeys the same equation of state.
*** For fermions, we have
1 = j\ =
1
,

j
ln[1 . oxp(,c
j
)[ .
In the thermodynamic limit, for free fermions, we can write

j
ln[1 . oxp(,c
j
)[ ~
\
(2)
3
1
_
0
4/
2
d/ ln
_
1 . oxp
_

,/
2
/
2
2:
__
1
=
\
(2)
3
_
_
_
4
8
/
3
ln
_
1 . oxp
_

,/
2
/
2
2:
__

1
0

2,
8
1
_
0
4/
2
d/
_
/
2
/
2
2:
__
.
1
oxp
_
,/
2
/
2
2:
_
1
_1
_
_
_
~
2,
8

j
c
j
.
1
oxp(,c
j
) 1
=
2,
8
l,
from which we prove that j\ = 2l,8. The same manipulations can be carried
out for bosons, but we should pay special attention to the / = 0 state. For the
classical gas, this result is trivial.
4. Consider a quantum ideal gas inside a cubic vessel of side 1, and suppose
that the orbitals of the particles are associated with wave functions that vanish
at the surfaces of the cube. Find the density of states in

/ space. In the
thermodynamic limit, show that we have the same expressions as calculated
with periodic boundary conditions.
5. An ideal gas of atoms of mass : is conned to a vessel of volume \ ,
at a given temperature T. Calculate the classical limit of the chemical potential
of this gas.
Now consider a two-dimensional gas of
A
free particles adsorbed on a
surface of area . The energy of an adsorbed particle is given by
c
A
=
1
2:
j
2
c
o
,
where j is the (two-dimensional) momentum, and c
o
0 is the binding energy
that keeps the particle stuck to the surface. In the classical limit, calculate the
chemical potential j
A
of the adsorbed gas.
The condition of equilibrium between the adsorbed particles and the particles
of the three-dimensional gas can be expressed in terms of the respective chemical
potentials. Use this condition to nd the surface density of adsorbed particles
as a function of temperature and pressure j of the surrounding gas.
*** In the thermodynamic limit, the chemical potential of the three-dimensional
gas is given by
j = /
B
T ln
_
8
3

\
_
,/
2
2:
_3=2
_
.
For the adsorbed gas, we have the classical limit
ln =

j
. oxp(,c
j
) = .

(2)
2
1
_
0
2/ oxp
_

,/
2
/
2
2:
,c
o
_
,
which yields the chemical potential
j
A
= /
B
T ln
_
4
2

_
,/
2
2:
__
c
o
.
2
From the physical requirement of equilibrium, j = j
A
, we obtain
A
, in
terms of temperature and pressure.
6. Obtain an expression for the entropy per particle, in terms of temperature
and density, for a classical ideal monatomic gas of particles of spin o adsorbed
on a surface of area . Obtain the expected values of H, H
2
, H
3
, where H is
the Hamiltonian of the system. What are the expressions of the second and
third moments of the Hamiltonian with respect to its average value?
7. Consider a homogeneous mixture of two ideal monatomic gases, at tem-
perature T, inside a container of volume \ . Suppose that there are
A
particles
of gas and
B
particles of gas 1. Write an expression for the grand parti-
tion function associated with this system (it should depend on T, \ , and the
chemical potentials j
A
and j
B
). In the classical limit, obtain expressions for
the canonical partition function, the Helmholtz free energy 1, and the pressure
j of the gas. Show that j = j
A
j
B
(Daltons law), where j
A
and j
B
are the
partial pressures of and 1, respectively.
8. Under some conditions, the amplitudes of vibration of a diatomic molecule
may be very large, with a certain degree of anharmonicity. In this case, the
vibrational energy levels are given by the approximate expression
c
n
=
_
:
1
2
_
/. r
_
:
1
2
_
2
/.,
where r is the parameter of anharmonicity. To rst order in r, obtain an
expression for the vibrational specic heat of this system.
*** Note that
ln7
v
= lno (c) r
c
o (c)
d
2
dc
2
o (c) O
_
r
2
_
,
where
o (c) =
1

n=0
oxp
_
c
_
:
1
2
__
=
_
2 sinh
c
2
_
1
,
with c = ,/.. We then have
n = /.
0
0c
ln7
v
and c = /
B
_
/.
/
B
T
_
2
0
2
0c
2
ln7
v
,
from which we calculate the rst-order correction to the specic heat,
^c = /
B
_
/.
/
B
T
_
2
r
d
2
dc
2
_
c
o (c)
d
2
dc
2
o (c)
_
.
3
9. The potential energy between atoms of a hydrogen molecule may be
described by the Morse potential,
\ (r) = \
o
_
oxp
_

2 (r r
o
)
a
_
2 oxp
_

r r
o
a
__
,
where \
o
= 7 10
19
J, r
o
= 8 10
11
m, and a = 10
11
m. Sketch a graph
of \ (r) versus r. Calculate the characteristic temperatures of vibration and
rotation to compare with experimental data (see table on Section 8.4).
*** Note that
d\
dr
= 0 for r = r
o
and
_
d
2
\
dr
2
_
ro
=
2\
o
a
2
0,
which shows the existence of a minimum at r = r
o
.
The characteristic temperature of rotation is given by
O
r
=
/
2
2/
B
1
=
/
2
2/
B
'r
2
o
,
where 1 is the moment of inertia and ' is the reduced mass of the hydrogen
molecule.
From the frequency of vibrations,
. =
_
2\
o
a
2
'
_
1=2
,
we write the characteristic temperature of vibrations,
O
v
=
/
/
B
_
2\
o
a
2
'
_
1=2
.
Now it is easy to check the numerical predictions.
4