2 Introduction and Basic Concepts

2.1 Systems of Identical Particles

The subject of the present discussion is the description of systems consisting of a large
number of identical particles. One such system is a gas consisting of a large number
of constituent molecules. Let us assume that the system under consideration occupies
the volume V and contains N noninteracting particles. The system is surrounded by
some medium and in general it is allowed to exchange both energy and particles with
the surrounding medium.
As the constituent particles of the system are microscopic objects, e.g., gas
molecules, their motion is ruled by the laws of quantum mechanics and they can only
occupy certain discrete energy levels. Let ni be the number of particles, which occupy
the energy levels within the energy interval (Ei , Ei + 1Ei ).
If the system is in an equilibrium state, the total number of particles in the system
is given by
X
N= ni , (2.1)
i

where the sum goes over all energy intervals (Ei , Ei + 1Ei ). The energy of each parti-
cle in the system is the sum of its kinetic and potential energies

Ei = Ti + i , (2.2)

and the total internal energy of the system can be written in the form
X
U= ni Ei . (2.3)
i

Above, we consider the so-called ideal systems that consist of mutually noninter-
acting particles. For the ideal systems, the potential energies i = i (Er) of the particles
are due to the influence of some external fields. For example, a gas under considera-
tion is normally under the influence of the Earth gravity. If the potential energies due
to external fields are nearly the same for all constituent particles, then such a system
is nearly homogeneous, that is, it has nearly uniform density. Under this condition,
the potential energies due to external fields are inessential for the description of the

Introductory Statistical Thermodynamics. DOI: 10.1016/B978-0-12-384956-4.00002-1

c 2011 Elsevier, Inc. All rights reserved.
Copyright
6 Quantum Description of Systems

systems macroscopic behavior. Thus, the macroscopic thermodynamic properties of

the system are determined by the kinetic energies of its constituent particles.
The simplest realizations of an ideal system are the gases of elementary particles
that have no internal structure or monatomic gases of inert elements (such as helium,
argon, neon, etc.), which internal structure can be ignored to a good approximation.
In such ideal gases, the constituent particles of the system can be treated as point-
like particles without an internal structure. Because of this, the kinetic energy of each
constituent particle is only due to the translational motion of the particle with velocity
Ev = Ev(t) and momentum pE = mEv. In general, the motion of the particles in an ideal gas
is a three-dimensional motion, which can be described by the Descartes co-ordinates
(x, y, z). Thus, an ideal gas has three translational degrees of freedom.
Sometimes the constituent molecules of a gas do have an internal structure and
cannot be treated as ideal point particles. For example, the molecules of common gases
in nature are often diatomic like hydrogen (H2 ), oxygen (O2 ), etc. Such molecules can
rotate and vibrate about their center of mass. If we analyze an individual molecule in a
co-ordinate system where its center of mass is at rest, i.e., in its center-of-mass frame,
then it has zero translational kinetic energy. In this frame, the energy of a molecule
includes only the energies of rotations and vibrations about its center of mass. In other
words, the gas has a number of additional degrees of freedom due to the rotations and
vibrations of the constituent molecules.

2.2 Quantum Description of Particles *)

In order to study the properties of the individual constituent particles and calculate
their kinetic energies, used to determine the macroscopic thermodynamic properties of
the system, an introduction to some basic concepts of quantum mechanics is needed.
According to the basic quantum-mechanical assumption, a particle of energy E and
momentum vector pE is associated with a wave of frequency and the wave vector
E . In other words, material particles have a dual wave-particle nature. The quantum-
mechanical relations between the particle quantities E and pE and the wave parameters
and E , respectively, are given by

E = ~, pE = ~E , (2.4)

where ~ = h/2 and h = 6.626068 1034 Js is the Planck constant. The motion of
such a matter wave is described by a complex wave function

= (Er, t). (2.5)

The squared magnitude of the wave function (2.5) is then interpreted as the probability
density of finding the particle in the space point Er = (x, y, z) at the time t. Since the
particle is located somewhere in the three-dimensional space, the absolute square of
the wave function (2.5) satisfies the following normalization condition
Z
|(Er, t)|2 d3 Er = 1, (2.6)
V
Introduction and Basic Concepts 7

where the integration is performed over the entire available three-dimensional space.
Unlike the classical mechanics, quantum mechanics can provide only the information
about the probabilities and expectation values of various physical quantities such as
the particle position, momentum, energy, etc. Thus, the expectation value of the energy
E is given by
Z
< E >= (Er, t)H(E
r, t)d3 Er, (2.7)
V

where (Er, t) is the complex conjugate of the wave function (Er, t), and H is the
energy operator or the Hamiltonian operator. The form of the operator H will be deter-
mined later. Likewise, the expectation value of the momentum vector pE is given by
Z
< pE >= (Er, t)pE (Er, t)d3 Er, (2.8)
V

where pE is the Momentum operator. In order to determine the forms of the energy and
momentum operators, we can use the wave function of a suitable plane wave, given by
 
i
Er it) = N exp ( pE Er Et) .
(Er, t) = N exp(iE (2.9)
~

Using the result (2.9), we see that

i~ (Er, t) = E(Er, t) = H(E
r, t), (2.10)
t
and

i~ (Er, t) = px (Er, t) = p x (Er, t)
x

i~ (Er, t) = py (Er, t) = p y (Er, t) (2.11)
y

i~ (Er, t) = pz (Er, t) = p z (Er, t).
z
The results (2.11) can be summarized in the following vector expression

i~(Er, t) = pE(Er, t) = pE (Er, t). (2.12)

Substituting (2.10) into (2.7) and (2.12) into (2.8), respectively, and using the normal-
ization condition (2.6), we obtain
Z
< E >= E |(Er, t)|2 d3 Er = E, (2.13)
V
8 Quantum Description of Systems

and
Z
< pE >= pE |(Er, t)|2 d3 Er = pE, (2.14)
V

as expected. In the simple case of the plane wave, the expectation values of the energy
and the momentum of the particle are equal to their exact classical values. From (2.10)
and (2.12), we can now identify the operators H and pE as follows:

= i~
H , pE = i~ . (2.15)
t
Since the wave functions (Er, t) are the functions of Er and t, i.e., we are working in the
ordinary three-dimensional representation, the operators of the coordinates and time
are simply equal to the coordinates and time. Thus, we have

x = x, y = y, z = z, t = t. (2.16)

Let us now recall the classical expression for the total energy of a single nonrelativistic
particle moving in the field of some general potential V = V(Er, t), i.e.,

p2
E= + V(Er, t). (2.17)
2m
Multiplying both sides with the wave function (Er, t), we obtain

p2
E(Er, t) = (Er, t) + V(Er, t)(Er, t). (2.18)
2m
Substituting the dynamical variables with their quantum-mechanical operators, we
obtain the following operator equation

p 2
(Er, t) =
H (Er, t) + V(
Er , t)(Er, t). (2.19)
2m
Substituting the operator definitions (2.15) and (2.16), we obtain the most general
time-dependent Schrodinger equation, in the following form

~2
i~ = 2 + V(Er, t), (2.20)
t 2m
where = (Er, t). The Schro dinger equation (2.20) is the fundamental equation of
quantum mechanics. In case of a stationary potential V(Er, t) = V(Er), i.e., a potential
that is constant in time, the wave function can be written in the form
 
iEt
(Er, t) = (Er) exp . (2.21)
~
Introduction and Basic Concepts 9

Substituting (2.21) into (2.20), we obtain the following time-independent Schro dinger
equation

~2 2
(Er) + V(Er) (Er) = E (Er). (2.22)
2m
In this book, we will only analyze the stationary phenomena, and we will, therefore,
use the time-independent Schro dinger equation (2.22) only.

2.3 Problems with Solutions *)

Problem
A commutator of two quantum-mechanical operators A and B is defined by
h i
B = A B B A.
A,
h i
t .
 
Calculate the commutators x, px and H,

Solution
The commutator x, px applied to an arbitrary wave function gives
 

 
x, px = i~ x, ,
 
(2.23)
x
or

 
x, px = i~ x (x) = i~ .
 
(2.24)
x x
Thus, we finally obtain the commutator

x, px = i~.
 
(2.25)
h i
Similarly, the commutator H, t applied to an arbitrary wave function gives

h i  
H, t = i~
, t , (2.26)
t
or

h i  
t = i~
H, (t) t = i~ . (2.27)
t t
Thus, we finally obtain the commutator
h i
t = i~.
H, (2.28)