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Chapter 1 Udel
Chapter 1 Udel
Introduction
1
2 Chapter 1.
This leads to the second role of statistical mechanics. It provides the link
between the microscopic properties of a many body system and its macroscopic
character. It is the link between the microscopic particle dynamics and interac-
tions, on the one hand, and the thermodynamic properties of the system made
up of these particles on the other. This link is made through the average process
via the distributions discussed above.
How do we specify microscopically the state of a large, many-particle
system? If we had one or two particles, we know from classical mechanics that
we need only specify the position ~xi and momentum p~i of the particles and this
completely determines (with the equations of motion) the present (and future)
behavior. We can regard ~xi and p~i as vectors to points in a three dimensional
configuration space and a three dimensional momentum space, respectively. If
we combine the two spaces, we will have a single point in a six dimensional
space. The combine position and momentum space is referred to as PHASE
SPACE. If the body we wish to specify contained only a single particle, this
point in the six dimensional phase space would specify the state of the system
completely.
We specify the state of a many-body system in the same way, by speci-
fying the ~xi and p~i of each of the i = 1 to NS bodies. We denote the number
of bodies in the system by NS to distinguish it from the number of systems in
the assembly. The dimensions of the phase space is now 6NS , six dimensions
for each of the NS particles. A point in this 6NS dimensional space completely
represents the state of the NS body system. In statistical mechanics we seek
the distribution of a collection of identical such systems over the possible en-
ergy states available to the systems. This distribution can be represented by a
distribution of representative points in the 6NS dimensional phase space or Γ
space.
in the assembly is also fixed. In doing this we will assume that initially there
is an equal probability of finding a system in any energy state or in any region
of phase space. That is, there is no a priori reason to choose one region over
another to begin our probability arguments. This assumption is discussed in
more detail in section 1.3.
In the Gibbs interpretation, the system is the actual solid, liquid or gas
containing many atoms that we wish to study. This system may, however, be
in a number of states. We naturally want to include and describe all possible
states of the system. To do this we construct an assembly of mental copies of
the system in its different states. Clearly, to represent all possible states in this
way each possible state of the system must appear at least once in the assembly.
Thus, here the assembly is the collection of mental copies. This assembly is also
often referred to as an ENSEMBLE in the Gibb’s method.
We might picture constructing our assembly of mental copies in the fol-
lowing way. Consider a large block of solid, say of copper, containing ∼ 1023
atoms. We could partition this block into 105 or 106 equal parts with each
part remaining large enough that it still represents the character of a block of
copper; that is each part has the same character of the initial system. Each
part can then be taken as the system. The idea is to select one of these parts
as our system and regard all the other parts as mental copies of this system.
As energy fluctuations take place in the block, energy is exchanged between the
one system selected and the mental copies. We assume loose mechanical contact
but good thermal contact between the copies so that the temperature will be
uniform in the block. In this way we may imagine our system immersed in a
heat bath made up of identical mental copies of the initial system. Clearly again
we must have enough mental copies so that each possible state, however rare, is
represented at least once in the assembly. The number of copies appearing in a
given state gives the probability of seeing the selected system in that state.
The last sentence is basically the statement if the ERGODIC HYPOTH-
ESIS. If we focus first on the selected system we could watch it for a long time.
During this time heat will be exchanged between the heat bath (the remainder
of the block) and the system’s energy will fluctuate. If we observe the system
for a long enough time T we should observe it in all its possible states. We
could then give the average value of a property A, say, of the system as
Z T
1
hAi = dts A(ts ) (1.1)
T 0
X
= ρ(s)A(s) (1.3)
s
where ρ(s) is the fraction of copies in the ensemble observed in state s. The
last average may be regarded as a space average over the whole block since we
could convert this to an integral over the block,
Z
1
hAi = drA(r) (1.4)
V
where V is the volume of the block. The ergodic hypothesis states that the time
and space ensemble averages in (1.1) and (1.4) are identical.
How do we specify the states s of our system, which is now composed of
a large number M of atoms or molecules? To do this we go back to dynamics
as noted above where we saw that we may specify the state of a single particle
by its momentum p~i and position ~xi . Once the initial momentum and position
of a single particle are given then, classically at least, the complete motion is
specified for all times by the eqution of motion the particle satisfies. We also
take ~xi and p~i as independent. This is obviously true in classical mechanics,
but in quantum mechanics ~xi and p~i can be specified only within Heisenberg’s
uncertainty limit
pi ∆~xi ≥ h3 .
∆~
In this way we specify the state of a particle by locating p~i and ~xi within a six
1
dimensional ”cube” of sides h 2 , where h = 6.023 × 10−27 erg. sec. We will
take this as the limit to which we attempt to specify ~xi and p~i and outside this
limit ~xi and p~i are regarded as statistically independent. The instantaneous
Chapter 1. 5
of phase space. The motion of the particles in the system can then be described
by the motion of this point through phase space. Particularly, if the NS ~xi and
p~i are fixed then the total energy of the system,
NS
X pi 2
E= + V (~xi . . . ~xn ),
i=1
2mi
case we are seeking the distribution of the N = NS particles over the possible
energy or momentum or velocity states. Once we have one distribution (e.g.
energy) we have the others since for a free particle the energy, momentum and
velocity are simply related by
p2i 1
²i = = mvi2 .
2m 2
We are able to regard the particles as the systems in a gas since they are
statistically independent units.
This choice is really arbitrary and most properties, we shall see, are independent
of this size. The absolute value of the entropy does, however, depend upon this
choice of cell size. We can also show that for the microscopic distributions we
seek, and particularly in classical cases, the cell size is not too large.
In Boltzmann’s statistical mechanics the cell size is h3 , since each system
is a single particle in a gas. In fact this cell is too small to contain a large num-
ber of atoms. For a gas at STP there is only one chance in ∼ 100, 000 that a cell
contains an atom. This means that we will have large statistical fluctuations
in the occupations of the cells (from 1 to 0 with rarely more than 1 in a cell).
Boltzmann’s combinatorial method depends mathematically on a uniform vari-
ation of occupation among adjacent cells. This apparent contradiction between
the cell size and the mathematical requirements of Boltzmann’s combinatorial
Chapter 1. 7
method lead many to criticize and dismiss his statistical mechanics. This prob-
lem can, however, be overcome by combining cells into groups large enough to
contain a large number of particles. This is valid since the observable particle
energy ² = p2 /2m varies slowly over the larger elements.
Given that the state of a system is represented by a point in phase space
in what cell do we place this point? That is, how do we weight or choose
the probability that a cell is occupied? The basic assumption of statistical
mechanics is that each region or cell of phase space is intrinsically equally likely
to be occupied. This is often referred to as the ”Equal A Priori Probability of all
regions of Phase Space”. This assumption is based on the fact that phase space
is everywhere the same and we have no reason to choose or favor one region over
another. It is based on a symmetry argument. By analogy if we had symmetric
dice, with each of the six sides identical, we would say that each side is equally
likely to appear facing up when the dice is thrown. Only if we weighted the faces
with some additional conditions would any faces be favored. We shall see that
when we weight our statistical arguments with external conditions that certain
regions of phase space become more heavily occupied than others. But before
these conditions are imposed, we assume that each region is intrinsically equally
likely to be occupied. Equally, before these conditions are imposed, each energy
state of the system is equally likely to be occupied.
1. The Classical Case: Here the particles are large enough or the tempera-
ture of a gas is high enough that classical mechanics accurately describes
the particles. In this case the de Broglie wavelength (the spread of each
particle in space) is much less than the inter-particle spacing (λ ¿ r) so
that each particle can be clearly distinguished from another. With this
distinguishability we can trace the path of a single particle through the
gas and identify it at each point. In this case we can distinguish between
states in which two particles have interchanged positions.
1. Classical Particles
• distinguishable
• leads to Maxwell-Boltzmann statistics
2. Bosons (integer spin particles)
• indistinguishable, can have any number in one state
• leads to Bose-Einstein statistics
3. Fermions ( 21 integer spin particles)
• indistinguishable, can have only one particle per state
• leads to Fermi-Dirac statistics
Finally, we note that we have considered a system of non-interacting par-
ticles to introduce the ideas of statistics. The three statistics hold, however,
for interacting particles as well. For classical particles, the particles remain
distinguishable when they interact. In the quantum case, the states a particle
can occupy are modified by the inter-particle interaction. Yet, the state of the
whole system is unchanged if we interchange two particles in their states. The
only change is that the states are more complicated to work out and are cer-
tainly not independent single particle states. The wave function describing the
whole system must again be either symmetric or anti-symmetric w.r.t. particle
interchange.
Secondly, a key idea is that of statistical independence. The mathematical
model we will treat is an assembly of N weakly interacting and statistically
independent systems. We will find that the probability of observing such a
system in energy state E is proportional to e−E/kT , the Boltzmann factor. What
constitutes a statistically independent system? Firstly, classical particles can
be independent because their wave functions are well localized compared to the
inter-particle spacing. That is, their de Broglie wavelength λ are much less than
the inter-particle spacing. Thus they are distinguishable and well isolated from
one another. If they also interact weakly or rarely then they can be regarded
as statistically independent. On the other hand quantum particles have widely
spread wave functions which overlap with the wave functions of other particles.
The de Broglie wavelength is long compared to the inter-particle spacing. In
this case the quantum particles can never be statistically independent even if
the inter-particle force is weak. They interact effectively via the overlap of
their wave functions. In this case the probability of observing the quantum
particles having energy ² is not given simply by the Boltzmann factor. Rather
this probability is given by the Fermi-Dirac distribution for Fermions and by
the Bose-Einstein distribution for Bosons.
For cases in which the particles of a body are not statistically indepen-
dent, either because they are classical and strongly interacting or because they
are quantum, we seek modes or excitations if the body which are independent.
These are then described by the Boltzmann factor. Examples are phonons in
solids or liquid 4 He or the ”quasi-particles” of liquid 3 He.