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of Statistical Mechanics

3.1 Introduction

The basic concepts of statistical mechanics will be discussed in this chapter. Statisti-

cal mechanics describes the thermodynamic behaviour of macroscopic systems from

the laws which govern the behaviour of the constituent elements at the microscopic

level. The microscopic elements can be atoms, molecules, magnetic or electric dipole

moments, etc. A macroscopic system, generally, is composed of a large number of

these elements (of the order of Avogadro number NA 6.0221023 per mole). Each

element may have a large number of internal degrees of freedom associated with dif-

ferent types of motion such as translation, rotation, vibration etc. The constituent

elements may interact with the external eld applied to the system. There can also

be very complex interaction among the constituent elements. In the thermodynamic

limit, the macroscopic properties of a thermodynamic system is thus determined

by the properties of the constituent molecules, their internal interactions as well as

interaction with external elds.

and number of elements N is dened as

N

lim N , lim V but = = nite. (3.1)

V

In this limit, the extensive parameters (such as volume, entropy, internal energy

etc.) of the system become directly proportional to the size of the system (N or V ),

while the intensive parameters (such as pressure, temperature, chemical potential,

etc.) become independent of the size of the system.

at equilibrium will be described by the laws which are governed by the behaviour

37

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

of the constituent elements of the system at the microscopic level. In the formalism

of statistical mechanics, a macroscopic property of a system is obtained by taking a

statistical average (or ensemble average) of the property over all possible mi-

crostates of the system at thermodynamic equilibrium. A microstate of a system

is obtained by specifying the states of all of its constituent elements. However, the

specication of microstates for classical and quantum particles are made dierently.

In this chapter, we will develop such a formalism for an isolated system for which

the internal energy E, volume V and number of particles N remain xed. The for-

malism will be extended to the closed and open systems in later chapters. First we

will describe the classical system and then the quantum system.

In classical mechanics, the state of a particle at any time instant is represented by

specifying its position coordinate q and the conjugate momentum p. In order to

specify the microstate of a system of classical particles, one then needs to specify

the position qi and the conjugate momentum pi of each and every constituent parti-

cles of the system where i varies from 1 to N for a N particle system. The state of a

N particle system is then completely and uniquely dened by 3N canonical coordi-

nates q1 , q2 , , q3N and 3N canonical momenta p1 , p, , p3N . These 6N variables

constitute a 6N -dimensional -space or phase space of the system. In other words,

each point in the phase space represents a microstate of the system. The volume

element of this 6N-dimensional -space is then given by

3N

d = dqi dpi . (3.2)

i=1

microstates for classical systems.

length L. The position coordinate q will be within 0 q L. The Hamiltonian of

a free particle is given by

p2

H= (3.3)

2m

where p is the momentum of the particle. For a given value of E the phase space is

described by

p = 2mE (3.4)

for any value of q within 0 to L. The macroscopic state of the system is given by

(E, N, L) with N = 1. The phase diagram of the particle is given in Fig.3.1(a) and

the area of the phase space enclosed by the phase lines is given by

38

Specication of microstates for classical system

p + (2mE) 1/2

p

E+ E

+ (2mE) 1/2

0 L q 0 L q

E

(2mE) 1/2

1/2

(2mE) E+ E

(a) (b)

Figure 3.1: (a) Accessible region of phase space for a free particle of mass m and energy

E in a one dimensional box of length L. (b) The same phase space for energy range E to

E + E.

the factor of two comes because p changes from 2mE to + 2mE. It is important

to note that the accessible region of phase space is represented by one dimensional

lines in a two dimensional phase space. In order to avoid this artifact a small width

E in energy E is considered which does not aect the nal results in the thermody-

namic limit. The particle then have energy between E and E + E. Consequently,

they will be conned in small strips of width p and the corresponding phase space

is shown in Fig.3.1(b). Therefore the accessible volume (in this case area) of the

phase space is given by

1/2

2m

(E, L; E) = E = L E (3.6)

E E

and the total number of microstates (E, L) must be proportional to the phase

space volume (E, L).

The Hamiltonian of the particle is given by

p2 1

H= + m 2 q 2 (3.7)

2m 2

where is the constant angular frequency of oscillation of the particle. For a given

energy E, the accessible region is given by the equation of an ellipse

q2 p2

+ =1 (3.8)

2E/(m 2) 2mE

as shown in Fig.3.2(a). The area of the phase space enclosed by the phase line is

given by

1/2

2E 2

(E) = 2

(2mE)1/2 = E (3.9)

m

39

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

p p

+ (2mE) 1/2

E

E+ E

0

+ (2E/m 2) 1/2

q

E

q

(2E/m 2) 1/2 0

(2mE) 1/2

(a) (b)

Figure 3.2: (a) Accessible region of phase space for a one dimensional harmonic oscillator

with energy E, mass m and spring constant k. (b) The same phase space for energy range

E to E + E.

material here and N = 1). Once again the phase space is represented by a one

dimensional line in a 2-dimensional phase space. Hence, we consider energy between

E to E + E and the accessible region is an elliptical shell as shown in Fig.3.2(b).

The phase space volume (in this case area) is then given by

2

(E; E) = E = E. (3.10)

E

Note that the accessible phase space volume (area) in this case is independent of

energy E. Again, the total number of microstates (E) will be proportional to the

phase space volume (E).

volume V . The Hamiltonian of the particle is given by

1

H= p2 + p2y + p2z (3.11)

2m x

where px , py and pz are the three components of the momentum vector. The phase

space is a 6-dimensional space and it is not possible to draw. For xed energy E,

the momentum of the particle is given by

and the constant energy surface will be the surface of a sphere of radius p in the

momentum space as it is shown in Fig.3.3. The phase space volume enclosed by the

constant energy surface is then given by

4 4

(E) = V p3 = V (2mE)3/2 . (3.13)

3 3

The volume of the accessible region of phase space for the energy between E and

40

Specication of microstates for classical system

pz

p

p

y

E

px E+

Figure 3.3: Accessible region of momentum space for a free particle of mass m in three

dimensions.

E + E is then

(E; E) = E = 2V (2m)3/2 E 1/2 E. (3.14)

E

The number of microstates (E, V ) again will be proportional to the phase space

volume (E, V ).

One may now consider several such examples. However, beyond two dimensions

it is dicult to draw the accessible region of phase space as demonstrated in Exam-

ple.3. Moreover, it would not be easy to calculate the hyper-volumes of accessible

region of higher dimensional phase space. For example, for a system of N free par-

ticles enclosed in a volume V one needs to calculate the volume of 3N-dimensional

sphere in the momentum space. We will discuss such cases in the next chapter.

However, the Hamiltonian of N free particles in a 3d box is

3N

p2i

H= (3.15)

i=1

2m

and the phase space volume within constant energy surfaces E and E + E will be

3N

3N 3N

(E, N ) = d qd p= dqi dpi . (3.16)

EHE+E i=1EHE+E

space volume (E, N, V ) and can be written as

makes a pure number. The constant 0 represents the volume required to specify

a single microstate in a 6N dimensional phase space. From dimensional analysis, it

could be seen that o should have dimension of [ML2 T 1 ]3N for a 6N dimensional

phase space. At the same time, [ML2 T 1 ] is the dimension of Planck constant h. We

41

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

then assign 0 = 1/h3N for a 6N dimensional phase space. Thus, there exists a large

number of microscopic states corresponding to a macroscopic state (E, N, V ) of an

isolated system. Since a macrostate corresponds to a large number of microstates,

it can be represented by the volume of a region in the phase space.

In order to study the time evolution of a phase point, consider a particular microstate

of the system and follow how it evolves in time. Finally one obtains a phase trajec-

tory. The time evolution of qi (t) and pi (t) is governed by the Hamiltons equations

of motion

H (q, p) H (q, p)

qi = and pi = , i = 1, 2, , 3N (3.18)

pi qi

where H(q, p) is the classical Hamiltonian of the system, q represents all 3N po-

sition coordinates, p represents all 3N momenta for a system of N particles in

3-dimensions. The locus of all the points in phase space satisfying the condition

H(q, p) = E, total xed energy of the system, denes the energy surface. However,

specication of such a large number of trajectories is virtually impossible. Instead,

let us specify the probability Pt of nding a trajectory in an element of phase space

volume d. The probability Pt can be obtained as

t

Pt = lim (3.19)

T T

where t is the time the system spends in d and T is the total time over which

the trajectory is tracked. If we consider any quantity X[q(t), p(t)] measured along

the trajectory, then its average should be given by

T

1

X = Xt Pt = lim X(t)dt. (3.20)

T T 0

t

The time average of a physical quantity is all one obtains by making a measurement

of that quantity on the given system, i.e.; the value one expects to obtain through

experiments.

An alternative statistical description of the above situation can be obtained by

considering various points in the relevant region of the phase space as representation

of dierent copies of the same system. The same system means systems which are

with the same macroscopic state (E, N, V ). Such collection of a large number of

replicas (or mental copies) of the system is called an ensemble. In an ensemble, all

its members then correspond to the given macrostate (E, N, V ) but to arbitrarily

42

Principle of ergodicity

dierent microstates (q, p). During time evolution of a system at a given macrostate,

the microstates of the system are supposed to pass through all these phase points,

the elements of the ensemble.

Now, we would like to calculate average value of a physical quantity X(q, p) of the

macroscopic system in hand. In order to do so, let us dene a density (or probability)

distribution function (q, p) for the phase space. (q, p) is the probability to nd

the system at a given point (q, p) of the phase space. Thus the distribution function

(q, p) integrated over the relevant region of the phase space must be given by

where the constant 0 is the same constant as dened in Eq.3.15 to make the value

of the integral a pure number. The average value of the physical quantity X(q, p)

then can be obtained as

X = 0 X(q, p)(q, p)d qd p= (3.22)

(q, p)d3N qd3N p

assuming that the distribution function (q, p) is an equilibrium distribution and has

no time dependence. Such an average is known as statistical or ensemble average.

The ensemble dene above is for xed E, N and V and hence for an isolated

system. Such an ensemble is known as microcanonical ensemble. For a closed

system which exchanges energy (not matter) with its surroundings will be described

by a dierent ensemble called canonical ensemble for which the corresponding

macrostate is given either by xed (N, V, T ) or by xed (N, P, T ). Similarly, for a

open system in which both energy and matter are exchanged between the system

and the surroundings will be described by an ensemble called grand canonical

ensemble for which the corresponding macrostate is given by (, V, T ). Later two

ensembles will be considered in appropriate later chapters.

From the above discussion, we have learnt that, given a dynamics and statistical

description, there are two dierent ways of calculating averages. If the evolution

dynamics is given, one obtains a time average given by

T

1

X = lim X(t)dt.

T T 0

(q, p), is known, one obtains a statistical or ensemble average

43

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

the two averages are indeed equal. That is known as ergodic hypothesis. Thus the

assertion of ergodicity hypothesis is that the statistical average and the time average

are equal:

X = X. (3.23)

Therefore, by calculating ensemble average of a physical quantity one obtains the

experimentally measured value of the same physical quantity.

In order to understand the implications of a time independent density distribution

(q, p), we need to study the time development of (q, p, t). The principle for deter-

mining the dynamics of is a conservation law, the conservation of the number of

phase points. In a given volume element d3N qd3N p around a phase point (q, p), the

number of phase points is given by

This number can change only if in the course of evolution some points enter or leave

the volume element across the surface which bounds it. Therefore, in absence of any

source and sink in the phase space, one has a local conservation law

d3N qd3N p = (v n)d = (v)d3N qd3N p (3.25)

t

where v = (q, p) is the velocity of the representative points in the phase space around

(q, p), represents the constant energy surface that encloses the relevant region of

phase space and n is the outwardly unit normal vector to the surface . Thus,

along a phase trajectory the continuity equation is given by

+ (v) = 0 (3.26)

t

where

3N

qi pi

(v) = qi + pi + +

i=1

qi pi qi pi

3N 3N

H H 2H 2H

= +

i=1

qi pi pi qi i=1

qi pi pi qi

3N

H H

= = {, H} (3.27)

i=1

qi pi pi qi

and the Hamiltonian H of the system. The total time derivative of the phase point

44

Equal a priori probability

d

= + {, H} = 0 (3.28)

dt t

that vanishes along the phase space trajectories. This is the Liouvilles theorem.

For a stationary ensemble which does not explicitly depend on time i.e.; /t =

0, it follows that

3N

H H

{, H} = = 0. (3.29)

i=1

qi pi pi qi

This means that is a constant of motion and depends only on conserved quantities.

The dependence of on (q, p) comes only through the explicit dependence on the

Hamiltonian, i.e.; = [H(q, p)]. In the present ensemble, the total energy E is the

conserved quantity. Hence, depends only on E and becomes independent of p and

q. That is,

(q, p) = constant. (3.30)

The condition of statistical equilibrium then requires no explicit time dependence

of the phase point density distribution (q, p) as well as a uniform distribution of

(q, p) over the relevant region of phase space. The value of (q, p) will, of course,

be zero outside the relevant region of phase space. However, note that in other

ensemble in which E is not constant it may have dierent explicit dependence on

Hamiltonian. For example for a canonical ensemble it can be shown that (q, p)

exp[H(q, p)/kB T ].

As the statistical equilibrium requires that the density distribution is uniform over

the relevant region of phase space and zero otherwise, it can be stated as

0 for E H(q, p) E + E

= (3.31)

0 otherwise

EH(q,p)E+E

1

for E H(q, p) E + E

(E)

= (3.33)

0 otherwise.

45

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

Therefore, every state in the relevant region of phase space dened by the xed

energy E and E + E has equal probability 1/(E). The relevant region of phase

space enclosed by the constant energy surfaces at E and E + E for an arbitrary

system is shown in Fig.3.4. In other words, any member of the ensemble is equally

likely to be found in any one of the large number of possible microstates. This

is known as the postulate of equal a priori probabilities for the various possible

microstates in a microcanonical ensemble.

p

E+ E

E

q

Figure 3.4: The shaded area represents the relevant region of phase space enclosed by

the constant energy surfaces at E and E + E.

The ensemble average of a physical quantity X(q, p) given in Eq.3.22 now can

be written as

X(q, p)(q, p)d3N qd3N p X(q, p)d3N qd3N p

X = = (3.34)

(q, p)d3N qd3N p d3N qd3N p

At statistical equilibrium corresponding to a uniform density distribution the

state of system must correspond to a state for which the number of microstates

(E, N, V ) maximizes as a function of its arguments. A physical system, left to

itself, proceeds naturally in a direction that enables it to assume an ever increasing

number of microstates until nally it settles down in a macrostate that aords the

largest possible number of microstates. This assertion has important consequences.

Consider two physical systems, 1 and 2 as shown in Fig.3.5. The systems 1 and

2 are independently in thermodynamic equilibrium at the macrostates (E1 , N1 , V1 )

and (E2 , N2 , V2 ) respectively. The number of microscopic states of the correspond-

ing systems are 1 (E1 , N1 , V1 ) and 2 (E2 , N2 , V2 ). Now the two systems are kept

in contact with each other but the combined system remains an isolated system.

Though the systems can exchange all three parameters energy, volume or number

of particles, the total energy, volume or number of particles remain constant for the

combined system. Thus the energy, the volume and the number of particles of the

46

Boltzmanns hypothesis

( E1 , V1 ,N1 ) ( E 2 , V2 , N 2)

1 ( E1 , V1 ,N1 ) 2 ( E 2 , V2 , N 2 )

Figure 3.5: Two physical systems 1 and 2 of volume V1 and V2 , number of particles N1

and N2 , and internal energy E1 and E2 respectively are in contact. However, the combined

system is isolated.

At any time t, the subsystem 1 is equally likely in any of the microstates 1 (E1 )

and the subsystem 2 is equally likely in any of the microstate 2 (E2 ). The combined

system is then equally likely to be in any of the microstate (E1 , E2 ) which must

be given by

= 1 (E1 , N1 , V1 )2 (E2 , N2 , V2 ). (3.36)

Let us suppose that an innitesimal amount of energy, volume and particles are

exchanged between the two subsystems keeping the total energy E, volume V and

number of particles N constant. Then, the dierential changes in these parameters

must vanish as given below

for an isolated system. If the combined system is now at equilibrium, the value of

will be maximum. Then the total derivative of (E, N, V ) is given by

1 2

d = 2 dE1 + 1 dE2

E1 V1 ,N1 E2 V2 ,N2

1 2

+ 2 dV1 + 1 dV2

V1 E1 ,N1 V2 E2 ,N2

1 2

+ 2 dN1 + 1 dN2 = 0. (3.38)

N1 E1 ,V1 N2 E2 ,V2

1 2 1 2

2 1 dE1 + 2 1 dV1

E1 V1 ,N1 E2 V2 ,N2 V1 E1 ,N1 V2 E2 ,N2

1 2

+ 2 1 dN1 = 0. (3.39)

N1 E1 ,V1 N2 E2 ,V2

47

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

1 1 1 2

For xed (N1 , V1 ) & (N2 , V2 ) : =

1 E1 V1 ,N1 2 E2 V2 ,N2

ln 1 ln 2

or, = . (3.40)

E1 V1 ,N1 E2 V2 ,N2

1 1 1 2

For xed (E1 , N1 ) & (E2 , N2 ) : =

1 V1 E1 ,N1 2 V2 E2 ,N2

ln 1 ln 2

or, = . (3.41)

V1 E1 ,N1 V2 E2 ,N2

1 1 1 2

For xed (E1 , V1 ) & (E2 , V2 ) : =

1 N1 V1 ,E1 2 N2 V2 ,E2

ln 1 ln 2

or, = . (3.42)

N1 V1 ,E1 N2 V2 ,E2

ln ln ln

= , = and = . (3.43)

E N,V V N,E N V,E

1 = 1 , 1 = 2 and 1 = 2 (3.44)

when energy, volume and number of particles of both the systems vary keeping the

total values of them constant.

Recalling the dierential form of the rst law of thermodynamics, one has

1 P

dS = dE + dV dN, (3.45)

T T T

and the thermodynamic parameters are given by

1 S P S S

= , = , = . (3.46)

T E V,N T V E,N T N E,V

S(E, N, V ) and a statistical quantity (E, N, V ), Boltzmann proposed

48

Classical ideal gas

manns hypothesis. Comparing Eq.3.43 with Eq.3.46, the parameters , and are

identied as

1 P

= , = and = . (3.48)

kB T kB T kB T

Therefore, if the exchange is such that all three macroscopic parameter of both the

systems vary to achieve equilibrium then the conditions of equilibrium are given by

T1 = T2 , P 1 = P2 and 1 = 2 , (3.49)

that these conditions are obtained here from statistical consideration. Therefore, if

we could calculate (E, N, V ), the number of microstates of an isolated system, one

could immediately derive the entropy S(E, N, V ), the fundamental thermodynamic

quantity, of the system and rest of the thermodynamic properties of the system can

be obtained just by taking dierent derivatives of S with respect to its arguments.

With the above denition of entropy (Eq.3.47) one can readily verify the exten-

sive property of entropy. Two isolated systems having microstates 1 and 2 , then

they have entropy S1 = kB ln 1 and S2 = kB ln 2 respectively. The two systems

are now combined together and they are allowed to interact keeping the combined

system as a whole isolated. The number of microstates of the combined system will

be = 1 2 and its entropy S will be given by

S = kB ln = kB ln 1 2 = kB ln 1 + kB ln 2 = S1 + S2 . (3.50)

The extensive property of entropy is thus built in there in the Boltzmanns hypoth-

esis. For natural processes in an isolated system the equilibrium corresponds to

maximum and hence the maximum of entropy S as required by the second law of

thermodynamics. It is important to note that the Boltzmann denition of entropy

does not contain any additive constant S0 . Therefore as T 0, the system is going

to be found in a unique state, its ground state, and the value of is going to be

1. Consequently, the entropy S 0. The statistical or Boltzmanns denition of

entropy thus provides a theoretical basis for the third law of thermodynamics.

energy E. The Hamiltonian of the system is given by

N

1

H= p2i = E (3.51)

2m i

49

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

where m is the mass of each molecule and p is the momentum of a molecule. The

phase space volume for E H is given by

(E, N, V ) = d3 q1 d3 qN d3 p1 d3 pN . (3.52)

EH

over p is equal to the volume

of a 3N dimensional sphere of radius R = 2mE. Therefore,

space. It can be shown that the volume of an N-dimensional sphere of radius R is

given by

N/2

N (R) = N N RN . (3.54)

2

( 2

)

Following the denition of volume of an N-dimensional sphere, one has

V N 3N/2

(E, N, V ) = 3N 3N

(2mE)3N/2 . (3.55)

2

( 2

)

The accessible volume of the phase space in the energy range E to E + E is then

given by

V N 3N/2 E

(E, N, V ) = E = 3N

(2mE)3N/2 (3.56)

E ( 2 ) E

and the number of accessible microstates (E, N, V ) is given by

N

1 3N/2 V E

(E, N, V ) = 3N (E, N, V ) = 3N (2mE)3N/2 . (3.57)

h ( 2 ) h3 E

one could obtain the entropy as

3/2

4mE 3

S(E, N, V ) = kB ln (E, N, V ) = NkB ln V + NkB (3.58)

3h2 N 2

1 S 3 NkB P S NkB

= = , = = (3.59)

T E N,V 2 E T V E,N V

3/2

S 4mE

and = = kB ln V (3.60)

T N E,V 3h2 N

50

Gibbs paradox and Over counting of microstates

Combining the relations in Eq.3.59, one could easily nd the equations of state

3 2

E = NkB T, P V = NkB T or P V = E. (3.61)

2 3

The equations of state are now derived from statistical mechanics. One also obtained

the expression for chemical potential without an unknown constant. However, note

the power of N in the expression of and compare with that of obtained in ther-

modynamics.

Consider an ideal gas in a chamber with a membrane separating the chamber in

two equal halves. Both the halves have equal volume V , internal energy E, and

number of molecules N. Now the membrane is removed and the system reaches

an equilibrium. What would be the change in entropy in this process? Since the

entropy of an ideal gas is given by

3/2

4mE 3

S = NkB ln V + NkB

3h2 N 2

V E 3/2 3 4m

= NkB ln + NS0 , S0 = kB 1 + ln , (3.62)

N 3/2 2 3h2

S = Sf Si

3 3

= (2N )kB ln(2V ) + (2N)kB ln(2E) (2N)kB ln(2N) + (2N)S0

2 2

3 3

2 NkB ln V + NkB ln E NkB ln N + NS0

2 2

= 2NkB ln 2. (3.63)

The entropy is thus extensive and the change S is positive. For removal of n such

membranes will lead to an increase in entropy by an amount S = nNkB ln 2 > 0.

However, this cannot be correct, since after the removal of the separating membranes

in the case of identical gases no macroscopically observable process happens at all.

Without any change we can bring back all the separating membranes again and

recover the initial situation. Thus, in the case of identical gases the removal of

the separating membranes is a reversible process and we must have S = 0. This

is known as Gibbs paradox. The paradox remains even after taking care of the

microscopic details in statistical mechanical approach of a microcanonical system in

estimating the entropy.

Since the gasses in the chambers are identical, the molecules during mixing can-

not be distinguished. However, we have calculated entropy presuming the particles

51

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

are distinguishable. Thus, we must have over counted the number of microstates in

evaluating (E, N, V ). Gibbs proposed a remedy to avoid over counting of states

and suggested that the number of accessible states should be

1 1

(E, N, V ) = d3N qd3N p (3.64)

N! h3N

EHE+E

where N! in the denominator would take care of the over counting of microstates and

eventually the indistinguishably of the gas molecules. Correspondingly, the entropy

of an isolated system of macrostate (E, N, V ) will be now

3/2 3/2

V 4mE 5 V E

S = NkB ln + NkB = NkB ln + NS0 , (3.65)

N 3h2 N 2 N N

with S0 = kB 52 + 23 ln 4m

3h2

. This is known as Sackur-Tetrode equation. Since

V /N and E/N both remain unchanged in this process, the change in entropy will

obviously be

S = 0.

Gibbs paradox is then resolved. However, note that the origin of Gibbs paradox is

associated with the indistinguishable property of the particles which is a property

of quantum particles.

The complete description of the state of a system in quantum mechanics is given by

the wave function |(r, t) , the solution of the Schrodinger equation

d|(r, t)

i = H|(r, t) (3.66)

dt

where H is the Hamilton operator of the system in a suitable Hilbert space. The

wave function |(r, t) is thus the quantum-mechanical analogue of the point in phase

space of classical statistical mechanics. Any dynamical state or the wave function

|(r, t) of the system can be expressed as a linear combination of the stationary

eigenstates |n as

|(r, t) = cn |n eiEn t/ (3.67)

n

where the coecients cn (t) dene a point in the (Hilbert) space of stationary eigen-

states |n . The stationary eigenstates |n are the solutions of the time independent

Schrodinger equation and is given by

H|n = En |n (3.68)

52

Specication of microstates of quantum systems

Let us consider a few examples and identify the microstates when the system is

composed of many quantum particles. Moreover, we need to calculate the number

of all possible such microstates.

Example 1: Consider localized magnetic ion of spin 1/2 and magnetic moment

in an external magnetic eld H. The energy of a single magnetic ion placed in an

external magnetic eld H, is given by

= H = (3.69)

+H for spin () anti parallel to H

Every ion then has two eigenstates each and can be represented as

1 0

= and = (3.70)

0 1

H () respectively. The single ion Hamiltonian operator in the energy basis is then

given by

1 0

H = H . (3.71)

0 1

Thus there are one microstate corresponding to E = H and one microstate

corresponding to +H.

an external magnetic eld H. The total Hamiltonian of the system will be

H = H1 + H2 + H3 (3.72)

where Hi is the single ion Hamiltonian. The eigenstates of the individual ions are:

i and i , i = 1, 2, 3. Since each ion has two states, there will be total eight spin

congurations: one conguration with all three up () with E = 3H, three

congurations with two up and one down () with E = H, three congurations

with two down and one up () with E = +H and one conguration with all

three down () with E = +3H. The wave function corresponding to a spin

conguration is just product of single ion eigenstates. Three up conguration is

given by 1 2 3 , three congurations with two up spins and one down spin are given

by 1 2 3 , 1 2 3 and 1 2 3 and similarly for other congurations. The energy

eigenvalues corresponding to these congurations can easily be veried by applying

the total Hamiltonian on the product state. All the congurations are schematically

represented in Fig.3.6 with their respective energy values and corresponding wave

functions. The number of macrostate corresponding to E/H = 3, 1, +1, +3 are

represented by .

53

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

H

3! 3!

= =

2! 1! 1! 2!

1 2 3 1 2 3

3! 1 2 3 1 2 3 =

3!

= 0! 3!

3! 0!

1 2 3 1 2 3 1 2 3 1 2 3

E/ H = 3 1 +1 +3

N!

(E, N) = (3.73)

n1 (E)!n2 (E)!

where N is the total number of ions and n1 , n2 are the number of ions in the up

state and the number of ions in the down state respectively. Here, N = 3 but

n1 and n2 have dierent values depending on the value of E. For E/H = 3,

n1 = 3, n2 = 0; for E/H = 1, n1 = 2, n2 = 1; for E/H = +1, n1 = 1, n2 = 2;

and for E/H = +3, n1 = 0, n2 = 3. Therefore, one has

E = n1 1 + n2 2 and N = n1 + n2 (3.74)

down states of a single ion respectively. Thus for a system of N such ions and xed

energy E, the number of ions in the up and down states are given by

1 E 1 E

n1 = N and n2 = N+ . (3.75)

2 H 2 H

N!

(E, N) = (3.76)

1 E 1 E

2

N H

! 2

N+ H

!

The denition of number of microstates can be generalized for a system having

many single particle eigenstates with xed energy E and total number of particle N

54

Specication of microstates of quantum systems

given by

E= nk k and N = nk (3.77)

k k

where nk is the number of particles on the kth eigenstate and k is the energy

eigenvalue of the kth state. The number of microstates will be then given by

N!

(E, N) = . (3.78)

nk !

k

mass m and frequency . The energy eigenvalues of such an oscillator is given by

1

n = n+ , where n = 0, 1, 2, (3.79)

2

1

n (x) = (a+ )n 0 (x),

n!

1 m 1/4 m 2

with a+ = (mx ip) and 0 (x) = e 2 x . (3.80)

2m

Thus, each value of n (including zero) there is then one microstate and for a xed

value of total energy E (compatible with Eq.3.79) there will be only one microstate.

Let us now consider a system of three such localized non-interacting one dimen-

sional quantum harmonic oscillators. If the total energy of the system is now xed

to, say, E = 27 , there will be two possible congurations. One is with one oscil-

lator in the ground (n = 0) state and two other oscillators in the rst excited state

and the second is with two oscillators in the ground (n = 0) state and one oscillator

in the second excited state. The microstates corresponding to these congurations

are given below

(1) (2) (3)

0 1 1

E

= 1 21 + 2 23 = 72 , = 1!2!

3!

= 3, microstates : (2) (1) (3)

0 1 1

(3) (1) (2)

0 1 1

(3.81)

(1) (2) (3)

0 0 2

E

= 2 2 + 1 2 = 2 , = 2!1! = 3, microstates : (1)

1 5 7 3! (3) (2)

0 0 2

(3) (2) (1)

0 0 2

However, for higher value of xed energy and large number of oscillators it is dicult

to keep track of microstates in this way. For N such oscillators, the total xed energy

55

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

E can be written as

1 1 1

E= n1 + + n2 + + + nN +

2 2 2

N

= (n1 + n2 + + nN ) +

2

N

= M + (3.82)

2

where M = n1 + n2 + + nN , ni = 0, 1, 2, , and i is the index for oscillators.

The integer M represents the total number of quanta of energy in the system.

The number of degenerate states can be obtained by calculating the number of ways

these M quanta are distributed among N localized oscillators. This is analogous

to the calculation of the distribution of M identical balls in N boxes as shown in

Fig.3.7.

1 2 3 4 N2 N1

walls.

(M + N 1)!

(3.83)

M!(N 1)!

separating walls, normalization is made by M! and (N 1)! because both the balls

and the separating walls are identical. For xed energy E and number of oscillators

N, the number of quanta is given by M = E/ N/2 and hence the number of

microstates is given by

E N

+ 2

1 !

(E, N) = E N

. (3.84)

2

!(N 1)!

7

2

+ 23 1 ! 4!

(E, N) = 7 3

= =6 (3.85)

2

2 !(3 1)! 2!2!

as expected.

potential well extended from x = 0 to x = L with zero potential inside the well and

56

Specication of microstates of quantum systems

2 d2 n (x)

= n n (x). (3.86)

2m dx2

The normalized eigenfunctions corresponding to the single particle states are given

by

2 nx

n (x) = sin (3.87)

L L

with the energy eigenvalues

h2 n2

n = with n = 1, 2, 3, . (3.88)

8mL2

So, corresponding to each value of n, there is a microstate. The microstates can be

represented by discrete points along the line n.

Let us now consider three such non-interacting particles in similar one dimen-

sional potential wells such that 0 x1 L, 0 x2 L, 0 x3 L. The

Schrodinger equation is given by

= n1 ,n2 ,n3 n1 ,n2 ,n3 (x1 , x2 , x3 ) (3.89)

2m dx2

whose solution is given by the product

h2

n1 ,n2 ,n3 = n1 + n2 + n3 = n2 + n22 + n23 with ni = 1, 2, 3, (3.91)

8mL2 1

where i is the index of a particle. Thus each microstate will be specied by specifying

the values of (n1 , n2 , n3 ).

3 6 9 12 15 18 21 E/

This is only possible if two particles are in the ground state (n = 1) and one particle

is in the rst excited state (n = 2). The number of possible congurations and

57

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

3! 1 (1)1 (2)2 (3)

2 2 2

E/ = 1 +1 +2 = 6, = = 3, (x1 , x2 , x3 ) = 1 (1)1 (3)2 (2) (3.92)

2!1!

1 (3)1 (2)2 (1)

The value of for 3 particles in one dimensional potential well is evaluated at a few

dierent values of E/ and they are presented in Fig.3.8. It can be seen that is a

very irregular function of the energy E. The eect will be more prominent in higher

dimensions and for large number of particles. The irregularities in is due to the

fact that the system can absorb or emit energy only in discrete quanta and can not

have arbitrary energy state.

potential well of sides Lx = Ly = Lz = L. The stationary states are given by

3/2

2 nx x ny y nz z

nx ,ny ,nz (x, y, z) = sin sin sin (3.93)

L L L L

h2

nx ,ny ,nz = n2 + n2y + n2z with nx , ny , nz = 1, 2, 3, (3.94)

8mL2 x

A microstate will be dened by a point in the (nx , ny , nz ) space. For xed energy

E, the vector n is given by

8mL2

n2 = n2x + n2y + n2z = E (3.95)

h2

and the constant energy surface will be the surface of a sphere of radius n. In Fig.3.9,

the grid points represent the microstates. The boundary of the constant energy

surface is shown by curved lines. The n-space volume enclosed by the constant

Figure 3.9: Grid points represent the microstates. The constant energy surface is

bounded by the curved lines.

58

Distinguishable and indistinguishable particles

3/2

1 4 1 4 8mL2

(E) = n3 = E . (3.96)

8 3 8 3 h2

1

g(E)E = E = 3 2V (2m)3/2 E 1/2 E. (3.97)

E h

This is nothing but the number of microstates within the energy range E to E + E.

Note that

1

g(E)E = 3 (E), (3.98)

h

where (E) is the classical phase space volume. Hence, the number of microstates

in classical statistics will be

1

(E) = 0 (E) = (E), (3.99)

h3

and the constant 0 is then given by 1/h3 for a 6-dimensional phase space. Thus, in

general, 0 = 1/hf for a 2f dimensional phase space.

In counting the number of microstates here it is presumed that the quantum

identical particles are distinguishable. However, this not correct quantum mechani-

cally. In general quantum particles are indistinguishable. Therefore it is necessary to

know how to classify the quantum particles as distinguishable or indistinguishable.

Two particles are identical if their intrinsic physical properties are exactly same. Po-

sition of a particle is a dynamical variable and hence not an intrinsic property rather

it is an extrinsic property. Therefore, two particles separated by a distance having

same intrinsic physical property are to be considered as identical particles. Identical

particles are distinguishable classically but indistinguishable quantum mechanically

when the wave packets of the particles are overlapping. But identical particles are

distinguishable also quantum mechanically when they are far apart (wave packets do

not overlap) or when there is some constant of motion by which the particles can be

distinguished. For example localized quantum particles are always distinguishable.

Quantum systems can reasonably be approximated as a classical system only

when the eect of Plancks constant h is negligible. That is,

qp h. (3.100)

molecules and r its mean separation from other identical molecules, then a clas-

59

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

rp h. (3.101)

Using the de Broglie wavelength, p = h/, one can dene the classical limit as

r . (3.102)

since is a measure of the spread of a molecule in space, it means that when the

above condition holds, the molecular wave functions do not overlap and they are

distinguished by their position.

The condition for the classical limit can be approximately represented in terms

of thermodynamic parameters. Consider that each molecule occupies a tiny cube of

side r and these tiny cubes ll the volume of the gas of N molecules,

1/3

V

r 3 N = V, r = . (3.103)

N

p2 3 h

= kB T, p = 3mkB T or, = (3.104)

2m 2 3mkB T

where kB is the Boltzmann constant. Detailed calculation shows that the thermal

h

wavelength = 3mk BT

. The condition for the classical limit Eq.3.102 can be

written as

1/3

V h 3mkB T

or, 1 (3.105)

N 3mkB T h1/3

where = N/V , the density of the gas. Thus the classical description is valid at

low density or at high temperature.

Under such conditions, the wave functions of N quantum particles are given by

product of individual wave functions. On the other hand, in the quantum limit

when the particles are indistinguishable, such description of product wave func-

tion fails. In this limit, the wave functions are either symmetric wave function or

anti-symmetric wave function. Distinguishable particles having product wave func-

tions follow Maxwell-Boltzmann statistics. Indistinguishable particles with sym-

metric wave function follow Bose-Einstein statistics whereas those are having anti-

symmetric wave function follow Fermi-Dirac statistics. The statistical mechanics of

indistinguishable particles will be discussed in a later chapter. Presently we will

consider distinguishable particles and develop statistical mechanical formalism for

them which eventually provide results of thermodynamic systems at low density or

at high temperature.

60

Quantum statistical average

Let us assume that the system is ergodic and the time average can be replaced by an

ensemble average over many quantum systems at the same instance. The state of a

quantum system can be prepared in many dierent ways. We will discuss dierent

situations one by one.

Say, the state of the system is given by a wave function in terms of a complete

ortho-normal basis states,

| = cm (t)|m (3.106)

m

where cm (t) are the complex amplitudes and | = 1. The quantum mechanical

expectation of an observable X is given by

m,n

Note that averaging here is performed over a very large number of measurements,

each performed on a system whose state |(r, t) is precisely specied by its known

amplitudes. The collection of such states in quantum mechanics is called a pure

ensemble. The quantum expectation can be rewritten as,

m,n

where 0mn = cn (t)cm (t). At the same time, let us dene a quantity 0 , the density

matrix operator for the pure ensemble, as

m,n m,n

m n

m,n m

for a pure ensemble. The properties of a density matrix 0 for a pure ensemble are

listed below:

61

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

elements of it will be zero except one element along the diagonal is 1.

4. n|0 |n = 0nn = |cn |2 0 for all n. Hence, 0 is positive denite (all positive

eigenvalues).

5. The time evolution of the density operator can be obtain considering time

dependent Schrodinger equation of the states,

| |

i = H| or i = |H (3.111)

t t

by

0 | | 1

= | | = | + | = H| | | |H

t t t t i

1 1

= H0 0 H = H, 0 . (3.112)

i i

Example: Consider a beam of electrons. Each electron has two spin eigenstates

either up | state or down | state, eigenstates of Sz .

(a) Say, the electrons are in the up | state with probability 1. Hence,

1 0

= | | = . (3.113)

0 0

Hence, the system is in a pure state. Obviously, Tr() = 1. All other properties can

also be tested easily.

(b) Say, the electrons are in the state 1 {| + | } state with probability 1. The

2

density matrix is given by

1 1

= {| + | } { | + |}

2 2

1 1 1 1

= | |+ | |+ | |+ | |

2 2 2 2

1/2 1/2

= . (3.114)

1/2 1/2

2

is given by

1 0

= . (3.115)

0 0

Hence, the system is in a pure state.

62

Quantum statistical average

One may wish to consider cases where the system is in any of number of dierent

states, with various probabilities. The system may be in state |1 with probability

P1 , in state |2 with probability P2 , and so forth. However, one must have

Ps = 1 and 1 Ps 0 (3.116)

s

for all s. These states may not be orthogonal and their number may exceed the di-

mensionality of the systems Hilbert space. Note that the situation is not equivalent

to say | = P1 |1 + P2 |2 + .

Let us assume that the system is in a state |s with probability Ps and it still

can be expressed as a linear combination of some complete basis {|m }. The state

|s then can be expressed as

m

where csm (t)s are complex amplitudes. Then the quantum expectation of an observ-

able X is given by

m,n

Now, the system can be in many such possible states |s . The ensemble average of

the quantum expectation of an observable X is then given by

X = Ps s |X|s

s

m,n s

= mn n|X|m (3.119)

m,n

where mn = s Ps csn (t) csm (t). Now, dene the density matrix as

m,n s m,n

s m n

(s)

= Ps |s s | = Ps 0 (3.120)

s s

(s)

where 0 is the pure state density matrix and mn = m||n . Then, the quantum

63

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

m,n m

the same denition as one obtained in the case of pure ensemble but with a dierent

density matrix. This formulation is advantageous in the sense that the density

matrix completely denes an ensemble of microstates of a quantum system and it

carries all the information that is available for a quantum statistical ensemble. Also,

we are free to choose the basis in which to work, so usually one can choose a basis

where either or X or both are diagonal. Let us now verify the properties of the

density matrix.

(s)

1. Since 0 is Hermitian, Ps is real, is Hermitian; = .

2. The trace of is

(s) (s)

Tr() = Tr Ps 0 = Ps Tr(0 ) = Ps = 1. (3.122)

s s s

3. The value of 2 is

(s) (s )

2 = Ps Ps 0 0

s s

= Ps Ps |s s |s s |

s s

= , (3.123)

in general.

4. The trace of 2 is

Tr(2 ) = Ps Ps | s |s |2

s s

Ps Ps s |s s |s

s s

Ps Ps

s s

1. (3.124)

5. The diagonal matrix elements nn of

nn = Ps n|s s |n = Ps |c(s)

n |

2

(3.125)

s s

64

Quantum statistical average

is the probability to nd the system in state |n , one of the basis states of the

systems Hilbert space. Hence, nn = n||n 0 or is non-negative. As

in classical systems, one has (q, p) 0. Note that the number of diagonal

terms is just the dimension of the systems Hilbert space but index s may have

arbitrarily dierent value. Similarly, the o-diagonal elements are

mn = Ps c(s)

m cn

(s)

(3.126)

s

are the coherences. If in any basis, is diagonal then in such basis all coher-

ences are zero.

(a) Say, the electrons in the beam are in the pure state | with probability 1/2

and in the pure state | with probability 1/2. The density matrix is then given by

1 1

= | |+ | |

2 2

1/2 0

= . (3.127)

0 1/2

The matrix is already diagonal and all diagonal elements are non zero. Hence, the

system is in a mixed state.

(b) Say, the electrons in the beam are in the state | with probability 1/2 and in

the state 12 {| + | } with probability 1/2. Then the density matrix is given by

1 1 1 1

= | | + {| + | } { | + |}

2 2 2 2

3 1 1 1

= | |+ | |+ | |+ | |

4 4 4 4

3/4 1/4

= . (3.128)

1/4 1/4

1/2 + 2/4 0

= (3.129)

0 1/2 2/4

diagonal elements are non zero and it represents mixed state.

65

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

The time development of the classical density distribution function (q, p) is given

by Liouville theorem. In order to have the time evolution of the density operator,

let us recall the time dependent Schrodinger equation of the states,

|s s |

i = H|s or i = s |H

t t

where H is Hamiltonian operator. Let us check the time evolution of the density

matrix for both pure and mixed states. The partial time derivative of is given by

= Ps |s s |

t t s

|s s |

= Ps s | + |s

s

t t

1

= Ps H|s s | |s s |H

i s

1

= H H

i

or, i = H, . (3.130)

t

This is the quantum analog of classical Liouville theorem and is known as von

Neumann equation. Therefore, as /t = 0 at equilibrium, one has

H, = 0. (3.131)

Thus, the equilibrium density operator has simultaneous eigenstates of the Hamil-

tonian. It also commutes with other operators which commutes with the Hamilto-

nian.

Now in the case of microcanonical ensemble, the internal energy E is xed. The

density matrix that include this constraint is given by

(H E)

(E) = (3.132)

(E)

energy eigenstates,

1

if En = E, and m = n

n||m = Ps n|s s |m = (3.133)

s

0 if En = E, or m = n.

This means that only eigenstates of the correct energy can appear in the wave

66

Entropy in terms of density matrix

function, and such states on average have the same amplitude, | n| |2 = 1/. This

is equivalent to the classical assumption of equal a priori probabilities. The o-

diagonal terms are zero means that degenerate eigenstates of energy E are combined

in a typical microstate with independent random phases. Note that the density

matrix is constructed on the single particle Hilbert space and the eigenstates are

the basis vectors. The number of diagonal elements are just the dimensionality of

the Hilbert space.

In quantum theory, the density matrix is necessary for any nontrivial calculation.

Since in certain representation the entropy solely depends on the diagonal elements of

the density matrix which are the probabilities of nding the system in certain states,

one can as well consider any problem with discrete probabilities {p1 , p2 , , pn }

which has nothing to do with quantum theory (they might refer to a problem even

in economics), and dene a matrix with the pi along the main diagonal:

p1 0 0

0 p2 0

= .. .. . . .. , (3.134)

. . . .

0 0 pn

{p1 , p2 , , pn } that one does with the density matrix . Thus the formalism devel-

oped for quantum theory can be used as well for any problem with discrete proba-

bilities. The expectation of any quantity Q = {q1 , q2 , , qn } can now be written

as Q = Tr(Q), where Q is a vector.

In microcanonical ensemble of distinguishable particles which are distributed

over discrete energy levels, one could construct a matrix with probability 1/ along

the diagonal for all the microstates corresponding to a given energy value since all

the states appear with equal a priori probability p = 1/. For example, the system

of three localized spin-1/2 magnetic ions has three microstates {| , | , | }

for a given energy value E = H where is the magnetic moment of each ion and

H is the external magnetic eld. The density matrix in the basis of these microstates

can be written as

1/3 0 0

= 0 1/3 0 . (3.135)

0 0 1/3

cal phase space. Let us calculate average of kB ln . Following the denition of

67

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

1

kB ln = 3N

{kB ln } d3N qd3N p

h

E+E

1 1 1

= 3N d3N qd3N p kB ln

h E

1

= kB ln

= kB ln

=S (3.136)

S = kB ln where is the density distribution in the classical phase space.

where is the density matrix for a quantum systems.

S = kB ln = kB Tr( ln ). (3.137)

series. It is convenient here to expand about A = 1 than about A = 0. Then one

can evaluate log A in terms of powers of A. Specically,

(1 )n

ln = (3.138)

n=1

n

representation, and ln are given by

1 0 0 ln 1 0 0

0 2 0 0 ln 2 0

= .. .. . . .. and ln = .. .. .. (3.139)

. .

. . . . . . . .

0 0 n 0 0 ln n

where n s are the eigenvalues of the density matrix. Hence the entropy S is obtained

as n

S = kB k ln k (3.140)

k=1

where the sum is over the energy eigenstates of a quantum system, n is dimension-

ality of its Hilbert space and k s are the eigenvalues of the density matrix .

Again, the denition of entropy can be generalized for the density matrix con-

structed for a discrete system where the microstates appear with denite probability.

68

Classical system versus quantum system

S = kB Tr( ln ) = kB s ln s (3.141)

s

where s = 1/ for all states s. But note that the sum here runs over all possible

states corresponding to a given energy and it is dierent from that given in Eq.3.140

where the sum runs over the eigenstates of a quantum system. Since s = 1/ in a

microcanonical ensemble, the entropy can as well be obtained as

ln

S = kB = kB ln , (3.142)

n=1

Example: Say, the ensemble of a system in some basis is represented by the density

matrix

1 0

= . (3.143)

0 0

The entropy of the system is given by

k

x0

Let us consider a system with mixed states. Say, the ensemble of such a system

in some basis is represented by the density matrix

1/2 0

= . (3.145)

0 1/2

1 1 1 1

S = kB k ln k = kB ln + ln = kB ln 2. (3.146)

2 2 2 2

k

Hence, entropy for a mixed state is nite and it will be always nite.

Finally let us put the denitions of statistical quantities of classical and quantum

systems together and have a comparison.

69

Chapter 3. Microcanonical Ensemble: Formalism of Statistical Mechanics

A point in the phase space. point in the Hilbert space.

3N

s

in the Hilbert space.

6N dimensional phase space.

1 3. Normalization: Tr() = 1.

3. Normalization: h3N

d = 1.

4. Number of microstates: = N ! .

d i ni

4. Number of microstates: = h3N

.

Xd 5. Ensemble average: X = Tr(X).

5. Ensemble average: X = h3N

.

6. Time evolution: i t = H, .

6. Time evolution: t

= {H, }.

f (H). have simultaneous eigenstates.

8. Fixed energy E: = 1/ if E 8. Fixed energy E: m||n = 1/ if

H E + E and zero otherwise. m = n, & En = E, otherwise zero.

9. Entropy: S = kB ln or 9. Entropy: S = kB Tr( ln ) or

S = kB ln . S = kB ln .

Therefore, calculating the number of microstates and obtaining entropy one can

study thermodynamic properties of an isolated system. Now we discuss a few ex-

amples.

Consider an isolated system of N localized non-interacting spin-1/2 magnetic ions

of magnetic moment in an external magnetic eld H. If the total energy of the

system is xed to E and under such condition n1 ions are in the up state (parallel

to H) and n2 ions are in the down state (anti-parallel to H). Thus, one has

E = n1 H + n2 H and N = n1 + n2 . (3.147)

tion is given by

N! N!

(E, N) = = . (3.148)

n1 (E)!n2 (E)! 1

N E

! 1

N+ E

!

2 H 2 H

70

Ideal Paramagnet

S(E, N) = kB ln

kB E 1 E

= NkB ln N N ln N

2 H 2 H

kB E 1 E

N+ ln N+ (3.149)

2 H 2 H

1 S kB 1 E kB 1 E

= = ln N ln N+ . (3.150)

T E N 2H 2 H 2H 2 H

1 exp( 2H

kB T

) H

E = NH = NH tanh . (3.151)

1 + exp( 2H

kB T

) kB T

Thus, the total magnetization M is given by

H

M = N tanh . (3.152)

kB T

M N2 H

T = = cosh2 (3.153)

H T kB T kB T

C

T (H = 0) = (3.154)

T

where C = N2 /kB , a positive constant.

71

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