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统计量子学
统计量子学
Dr. A. J. Macfarlane1
Lent 1998
1 A
LT
EXed by Paul Metcalfe – comments to soc-archim-notes@lists.cam.ac.uk.
Revision: 1.10
Date: 1998-06-03 20:13:39+01
Introduction v
2 Thermodynamics 11
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.2 Applications of dE = T dS − P dV . . . . . . . . . . . . . . . . . . 12
2.2.1 Integrability conditions . . . . . . . . . . . . . . . . . . . . . 12
2.2.2 Specific heats . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2.3 Adiabatic changes . . . . . . . . . . . . . . . . . . . . . . . 14
2.2.4 Entropy of n moles of ideal gas . . . . . . . . . . . . . . . . 14
2.2.5 van der Waal’s equation . . . . . . . . . . . . . . . . . . . . 15
2.2.6 The Joule effect . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.3 Some thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.3.1 The second law . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.4 Heat flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
iii
iv CONTENTS
Approximations 37
Introduction
These notes are based on the course “Statistical Physics” given by Dr. A. J. Macfarlane
in Cambridge in the Lent Term 1998. These typeset notes are totally unconnected
with Dr. Macfarlane. The recommended books for this course are discussed in the
bibliography.
Other sets of notes are available for different courses. At the time of typing these
courses were:
Probability Discrete Mathematics
Analysis Further Analysis
Methods Quantum Mechanics
Fluid Dynamics 1 Quadratic Mathematics
Geometry Dynamics of D.E.’s
Foundations of QM Electrodynamics
Methods of Math. Phys Fluid Dynamics 2
Waves (etc.) Statistical Physics
General Relativity Dynamical Systems
v
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edited them and the date of any change.
The latter are not states in the quantum mechanical sense, but do involve the vast
numbers of microstates.
The ergodic hypothesis (which is provable for some systems) is that S passes in
time through all its possible states compatible with its state of thermodynamic equilib-
rium. This allows us to replace time averages for a single system S with averages at a
fixed time over a suitable ensemble E of systems, each identical to S in its macroscopic
properties. The most probable state of E reveals which microstates of S contribute to its
macroscopic states of thermodynamic equilibrium and yield excellent approximations
to the values of its thermodynamic variables.
Let E, N be the total energy and total number of particles of S respectively. One
meets three types of ensemble.
1
2 CHAPTER 1. QUANTUM STATISTICAL MECHANICS
• canonical : each member of E has N particles but E is not fixed, although the
average total energy is time independent.
• grand : neither E nor N is fixed, although the averages are.
For the latter two, fluctuations about the average values are found to be very small
and all three types of ensemble give the same thermal physics. This course studies
mainly canonical ensembles. We will do systems with identical bosons/fermions via
the grand ensemble for technical simplicity.
The fact that averaging procedures give reliable estimates of values of physical
variables and apparently different procedures yield equivalent results is due to the effect
of the very large number of particles involved. For instance, consider the probability
pm of obtaining N/2 + m heads from N coin tosses.
r
−N N 2 − 2m2
pm = 2 N ∼ e N ,
2 +m πN
X X
ai = A and ai Ei = AE. (1.1)
i i
A A − a1 A!
W (a) = ··· = Q .
a1 a2 i ai !
We assign equal a priori probability to each way of realising each possible con-
figuration of E and thus there is a probability proportional to W (a) of realising the
configuration {ai }.
1 log n! 1
∼ n log n − n + 2
log 2πn
1.2. CANONICAL ENSEMBLE 3
We will associate the state of thermodynamic equilibrium of S (for the fixed values
N , V , E) with the configuration of E that is most probable in the presence of the
constraints (1.1).
To compute this suppose A 0 such that ai 0 (negligible probability attaches
to configurations where this fails). For large n, Stirling’s formula allows log n! ∼
n (log n − 1) and so
X X
log W ∼ A log A − A − ai (log ai − 1) = A log A − ai log ai .
i i
We seek to maximise this subject to the constraints (1.1). We use two Lagrange
multipliers α and β and solve
!
∂ X X
0= log W − α ai − β ai Ei
∂aj i i
aj = e−1−α−βEj . (1.2)
X X
Z= e−βEi ≡ Ω(Ej )e−βEj , (1.3)
i Ej
ai 1
ρi = = e−βEi . (1.4)
A Z
This is the Boltzmann distribution, and may be thought of as the probability of
finding |ii in the state of thermodynamic equilibrium.
We define the average hXi of a physical variable X taking the value Xi in the state
|ii by
X
hXi = ρi X i . (1.5)
i
1 P
For instance hEi = A i ai Ei = E (reassuringly).
Z is very important. It leads directly from quantum mechanical data to calculation
of the thermodynamic variables for S in thermodynamic equilibrium. For instance,
∂ log Z
E=− . (1.6)
∂β
4 CHAPTER 1. QUANTUM STATISTICAL MECHANICS
2
1 ∂2Z
∂E 1 ∂Z 2
=− + 2 = −hE 2 i + hEi2 = − (∆E) .
∂β Z ∂β 2 Z ∂β
1.3 Temperature
Given two systems Sa and Sb with fixed volumes Va , Vb and numbers of particles Na ,
Nb respectively we place them in contact to form a composite system Sab such that
energy can pass from one to the other and a state of thermodynamic equilibrium is
reached. We make a canonical ensemble Eab for Sab by distributing A replicas of Sa
and A replicas of Sb independently across the A members of Eab so that each member
of Eab has a component of type Sab .
Suppose that Sa has microstates |ii of energy Eai , Sb has microstates |σi of energy
Ebσ and Sab has microstates |i, σi of energy Eai + Ebσ .2
Suppose the |ii occurs ai times, |σi occurs bi times and |i, σi occurs ciσ times in
Eab . Then we have
X X
ai = A bσ = A (1.7)
i σ
X X X
ai = ciσ bσ = ciσ ciσ = A (1.8)
σ i iσ
X X
AE = ai Eai + bσ Ebσ (1.9)
i σ
X
AE = ciσ (Eai + Ebσ ) . (1.10)
iσ
A!
W (c) ∝ Q (1.11)
iσ ciσ !
A! A!
W (a)W (b) ∝ Q Q (1.12)
i a i ! σ bσ !
ciσ
ciσ = e−1−αab −β(Eai +Ebσ ) ρiσ = .
A
We can also maximise (1.12) subject to (1.7) and (1.9) to get
ai
ai = e−1−αa −βEai ρi =
A
bσ
bσ = e−1−αb −βEbσ ρσ = .
A
Defining
X X X
Zab (β) = e−β(Eai +Ebσ ) Za (β) = e−βEai Zb (β) = e−βEbσ
iσ i σ
we see that Zab (β) = Za (β)Zb (β) and ρiσ = ρi ρσ . A common value for β
characterises the state of thermal equilibrium of Sab and it is natural to assume that β
is some function of temperature T and that the average energy (the energy) of a system
is a function of N , V and T .
1
We define T by β = kT where k is a constant.
As this argument applies to any two systems, k should be a universal constant
(Boltzmann’s constant) the same for all systems when a universal definition of T is
used. We will define T for a standard system (a thermometer) and for other systems by
putting them into a state of thermal equilibrium with our standard system.
Recall the ideal gas law, P V = N kT for a sample of N molecules.3 k is the same
because equal volumes of all gases at fixed temperature and pressure are observed to
have the same number of molecules. T is in degrees Kelvin.
P Consider next changes Pin which the ρi are allowed to vary. Then δE = −P δV +
i Ei δρ i , and note that i δρi = 0.
Define the entropy
k
S= log Wmax that is, W at thermal equilibrium
A !
k X
= A log A − ai log ai
A i
! (1.14)
k X X
= A log A − ai log ρi − log A ai
A i i
X
= −k ρi log ρi at thermal equilibrium.
i
We see that
X 1
δS = −k δρi log ρi + ρi log ρi
ρi
X
= −k δρi (−βEi − log Z + 1)
1 X
= Ei δρi
T i
P
and thus i Ei δρi = T δS. We have defined S such that
We might regard this as arising from the comparison of ensembles with infinitesi-
mally different states of thermal equilibrium. (1.15) states the First Law of Thermody-
namics4 , written in the form
dE = δQ + δW, (1.16)
∂E ∂E
(1.15) also shows that T = and P = − ∂V
∂S .
2
For a gas of spinless particles, E = i Ei ρi ∝ V − 3 and so P = 32 VE , giving
P
P V = 32 E. Combined with the result for a perfect gas, E = 23 N kT (see later), we
have Boyle’s law P V = N kT .
We want to be able to calculate S from the partition function. Now, at thermal
equilibrium,
X
S = −k ρi log ρi
i
X
= −k ρi (−βEi − log Z)
i
1
= E + k log Z.
T
Define the free energy F = E − T S, then
F = − β1 log Z. (1.17)
Also,
1 ∂ log Z ∂ ∂F
S=− + k log Z = (kT log Z) = − . (1.18)
T ∂β ∂T ∂T
We have a very tangible definition of S, as proportional to log Wmax , where Wmax
is the number of microstates of S contributing to the state of thermal equilibrium.
Given the partition function (1.3), we can calculate the thermodynamic variables
in a state of thermal equilibrium, P (by (1.13)), E (by (1.6)), F (by (1.17)) and S (by
(1.18)).
Let Z ≡ ZN describe the sum over states of a gas of N very weakly interacting
particles. If these are supposed independent (distinguishable) then Z = z N , where
z is the “one particle partition function”. This allows easy calculations, but fails for
systems of identical (indistinguishable) bosons or fermions. For the latter it seems best
to use grand ensemble methods.
Later we will consider a gas of diatomic molecules, H = HT + Hrot + Hvib , where
HT describes the centre of mass motion, Hrot describes rotation about the centre of
mass and Hvib describes vibration along the axis. We see that the one particle partition
function is z = zT zrot zvib .
8 CHAPTER 1. QUANTUM STATISTICAL MECHANICS
Z 3
X L
→ d3 k (1.19)
i
2π
V
Z
= 4πk 2 dk
(2π)3
Z 1
V 2m 2 2md
= 4π
(2π)3 ~2 2~2
32 Z
2m 1
= 2πV 2 d (1.20)
h
Z
= dg().
gives the density of states. We use (1.20) in isotropic contexts, but (1.19) is needed
in kinetic theory.
In two dimensions we consider a square of side L and A = L2 enters in the rôle of
2m
V . We find that g() = h2 gS 2πA is independent of .
1.5. TOWARDS APPLICATIONS 9
21
For relativistic particles of rest mass m we have = m2 c4 + ~k 2 c2 and use
(1.19) to get
Z ∞
4π
Z Z
3 2
1
d k = 4πk dk = d 2 − m2 c4 2 . (1.21)
(~c)3 mc2
We also supply a factor gS = 2S + 1 for a particle of spin S with nonzero rest
mass. For photons, m = 0, gS = 2 and so
3 Z ∞ ∞
V 4π 8πV
X Z
→2 2 d = ν 2 dν. (1.22)
i
(2π)3 ~c 0 c3 0
1 2m
32
where g() = DV 2 and D = 4π h2 . Setting y = β we get
∞ 32
2mπkT
Z
3 1
−y
z = DV (kT ) 2
dy y e2 =V . (1.23)
0 h2
This is the classical result: there is an energy 12 kT associated with each degree of
freedom of each particle. Combining with P V = 23 E we get P V = N kT .
Thermodynamics
2.1 Introduction
Consider a volume V of gas with a fixed number N of particles. The state of thermal
equilibrium of this gas is characterised by T and V .
Our work with quantum statistical mechanics has produced some concepts natu-
rally:
• E: the total energy of the system, which arose as the average energy and has
negligible fluctuations.
• S: the entropy. This has a clear significance as the number of microstates con-
tributing to the macrostate of thermal equilibrium.
• equations of state: for instance P V = N kT .
• dE = T dS − P dV , which is true for any thermodynamic change between two
infinitesimally close states of thermodynamic equilibrium.
All thermodynamic variables for the sample of gas we are talking about can be
regarded as a function of two suitably chosen independent variables. In the case of the
energy, E arises as E(S, V ).
We also found that dE = δQ + δW , where δQ is the heat supplied to the system
and δW is the work done on the system.
For finite changes from the initial to the final state conservation of energy gives
∆E = ∆Q + ∆W . This is the first law of thermodynamics, equivalent to the conser-
vation of energy.
Suppose we change from a state with E1 (S1 , V2 ) to E2 (S2 , V2 ). In general, we
expect
Z V2
∆W ≥ − P dV
V1
11
12 CHAPTER 2. THERMODYNAMICS
These inequalities hold as equalities for reversible changes, that is changes which
are quasi-static and non-dissipative.
Quasi-static changes are changes which are done so slowly as to pass through states
arbitrarily close to a state of thermodynamic equilibrium, so that all thermodynamic
variables are well-defined throughout the change.
Some (obvious) irreversible processes are fast piston movement, free expansion of
a gas into a vacuum and the mixing of samples of different gases.
In induced/allowed changes in real life with δQ = 0, δS > 0 and so the entropy
increases.
2.2 Applications of dE = T dS − P dV
2.2.1 Integrability conditions
The internal energy E is seen as E(S, V ) within
∂E ∂E
dE = T dS − P dV = dS +
∂S V ∂V S
∂2 E
Thus T = ∂E ∂E
∂S V and P = − ∂V S . dE is an exact differential, so ∂S∂V =
∂2E
∂V ∂S and
∂P ∂T
− =
∂S V ∂V S
∂z ∂z
δz = δx + δy and hence
∂x y ∂y x
∂x ∂z
1= and
∂z y ∂x y
∂x ∂z ∂z
0= + .
∂y z ∂x y ∂y x
2.2. APPLICATIONS OF DE = T DS − P DV 13
∂x ∂z
=1
∂z y ∂x y
(2.1)
∂x ∂y ∂x
= −1.
∂y z ∂x z ∂z y
∂E ∂E
T dS = dT + dV + P dV and so
∂T V ∂V T
∂S ∂E
T = and
∂T V ∂T V
∂S ∂E
T = + P.
∂V T ∂V T
∂2 S ∂2S
Also, we know that ∂T ∂V = ∂V ∂T and so
∂E ∂P
=T − P.
∂V T ∂T V
∂E
For a perfect gas, P V = N kT and so ∂V T
= 0. Thus E is a function of T only.
Given the laws of thermodynamics we need two inputs from experiment to specify
all thermodynamic variables completely. For instance, for a perfect gas we need the
equation of state and E = CT .
R is called the gas constant and is the same for all ideal gases. In fact, all gases are
essentially ideal at sufficiently low density.
For a sample of 1 mole of ideal gas we define the specific heat (or heat capacity per
mole) using δQ = T dS under suitable conditions.
∂S ∂S
Define CV = T ∂T V
, the specific heat at constant volume and CP = T ∂T P
,
the specific heat at constant pressure. Now
T dS = dE + P dV = dH − V dP
and so
14 CHAPTER 2. THERMODYNAMICS
∂S ∂E
CV = T =
∂T V ∂T V
(2.3)
∂H
CP = .
∂T P
For one mole of ideal gas we know that E = CT and so C = CV . To find CP we
need to use P and T as the independent variables.
Now
∂S ∂S
dS = dT + dV
∂T V ∂V T
∂S ∂S ∂V ∂V
= dT + dT + dP .
∂T V ∂V T ∂T P ∂P T
∂S ∂S ∂S ∂V
Thus ∂T P
= ∂T V
+ ∂V T ∂T P
and so
∂S ∂V ∂V ∂P
CP = CV + T = CV + T . (2.4)
∂V T ∂T P ∂T P ∂T V
This allows the calculation of CP − CV from the equation of state: for an ideal gas
CP − CV = R. Define the ratio of specific heats γ = C CP
V
. Note that γ = CVC+R
V
>1
for an ideal gas.
Statistical mechanics gives CV = 23 R, 52 R, . . . (for monatomic, diatomic (etc)
gases). Thus γ = 53 , 75 , . . . .
n2 A
P + 2 (V − nB) = nRT, (2.5)
V
where A, B and R are strictly positive constants.
• Molecules are not treated as point particles, and as P → ∞ at constant T , V →
nB, which is the residual volume of all the molecules.
2 2
• P + nV 2A reduces the real gas pressure by an amount nV 2A , due to intermolecular
attractive forces. If these are short range then the smaller V is the more important
these become.
Consider the apparatus shown, with adiathermal walls and containing n moles of gas at
volume V1 , pressure P1 and temperature T1 . Pull back the partition and allow the gas
to expand (irreversibly) into the total volume V2 , and then to reach a state of thermal
equilibrium specified by P2 , V2 and T2 .
As δQ = 0 (adiathermal) and δW = 0 (no work is done), dE = 0 and so for a
perfect gas
T2 = T1 and S2 − S1 = nR log VV21 > 0 for V2 > V1 .
For a van der Waal’s gas we still have dE = 0 (which is true in general) and so E
stays constant. Now
∂E
∂T ∂V T
=− ∂E
∂V E ∂T V
− T ∂P
P ∂T V
=
nCV
2
n A 1
=− 2 for van der Waal’s gas
V nCV
< 0.
We can show that CV is independent of V for a van der Waal’s gas and we suppose
that CV is also approximately independent of T . We can now integrate this equation to
get
nA 1 1
T2 − T1 = − < 0.
CV V2 V1
T decreases because some of the molecular kinetic energy is lost in the expansion
against attractive intermolecular forces.
16 CHAPTER 2. THERMODYNAMICS
Z V2
∆Q + ∆W = 0 ⇒ ∆Q = −∆W = P dV = nRT log VV12 .
V1
Thus ∆W > 0 for compression (V2 < V1 ) and ∆Q < 0. Heat is given out to B
by S. Now ∆S = nR log VV21 and so the entropy of S decreases. However, because the
isolated universe of S and B has ∆S = 0 the entropy of B must increase.
Take a sample S of perfect gas around a closed Carnot cycle by means of adiabatics
and isothermals (T2 > T1 ). On AB the heat bath at T2 supplies heat ∆Q2 > 0 to S at
temperature T2 . On CD the heat bath at T1 supplies heat ∆Q1 < 0 to S at temperature
T1 .
E = E(T ) is unchanged over one complete cycle so that the work done in a cycle
by S is −W = ∆Q1 + ∆Q2 by the first law (as δQ = 0 on adiabatics).
This agrees with the Kelvin statement of the second law, (−∆Q1 ) > 0 of heat is
wasted at the low temperature heat bath. The efficiency η is defined
−W ∆Q1
η= =1+ < 1.
∆Q2 ∆Q2
T2 −T1
Thus η = T2 , and clearly 0 < η < 1. This can be generalised to other cycles.
1 You can’t break even either... (see footnote on page 6)
2.4. HEAT FLOW 17
x1 (T1 − T ) + x2 (T2 − T ) = 0
and we can solve for T . As for the entropy, ∆S1,2 = x1,2 log TT1,2 and ∆S1 +∆S2 ≥ 0.
18 CHAPTER 2. THERMODYNAMICS
Chapter 3
We have thus fixed the average energy and number of particles of members of the
ensemble. Each configuration {ai } of G defines a state of the ensemble and we assign to
each configuration equal a priori probability. We associate the state of thermodynamic
equilibrium of S with the most probable configuration of G in the presence of our
constraints. We find this by maximising the same log W as before to get
!
∂ X X X
0= log W − α ai − β ai Ei − γ ai N i .
∂ai i i i
where we have defined the chemical potential µ by βµ = −γ. We now define the
grand partition function
X
Z= e−β(Ei −µNi ) . (3.1)
i
ai e−β(Ei −µNi )
ρi = = .
A Z
19
20 CHAPTER 3. GRAND ENSEMBLE METHODS
and Ē = E and N̄ = N (which is, on the whole, a good thing). As before we can
use Z to calculate thermodynamic variables:
1∂ log Z
N= , (3.2)
β ∂µ β,V
∂ log Z
E − µN = − . (3.3)
∂β µ,V
X ∂Ei 1 ∂ log Z
P =− ρi = . (3.4)
i
∂V β ∂V β,µ
k X
S=− log Wmax = −k ρi log ρi
A i
gives that
X X 1
δS = −k δρi log ρi − ρi δρi
i i
ρi
X
= −k δρi (−β(Ei − µNi ) − log Z) .
i
T δS = δE + P δV − µδN, (3.5)
yielding the first law dE = δQ + δWmech + δWchem , where δWchem = µδN is the
work done in adding δN particles to the system S. The chemical potential is therefore
given by
∂E
µ= . (3.6)
∂N S,V
3.2. SYSTEMS OF NON-INTERACTING IDENTICAL PARTICLES 21
∂kT log Z
S= . (3.8)
∂T µ,V
A similar argument to that used to define temperature in 1.3 gives that two systems
placed in thermal and “diffusive” contact will reach a thermodynamic equilibrium char-
1
acterised by common values of β = kT and µ.
We keep the idea that at fixed NA , NB energy flows from the system with the
higher temperature to that with the lower temperature until thermodynamic equilibrium
is reached. We add that if the contact allows the diffusion of particles then in the state
of thermodynamic equilibrium with constant µ there is (on average) no diffusion.
We return to the first law, dE = T dS − P dV + µdN . We can view E as a function
of S, V and N , and when (as for many large systems), E, S and V are extensive we
get
E(λS, λV, λN ) = λE(S, V, N )
and so
∂E ∂E ∂E
E=S +V +N
∂S V,N ∂V S,N ∂N S,V
= T S − P V + µN.
We define the grand potential Ω for a state of thermodynamic equilibrium by
Ω = E − T S − µN
= E − µN − (E − µN + kT log Z)
= −kT log Z.
~2 2
En = |n| .
2mL2
For identical bosons we cannot use wavefunctions φ1 (x1 )φ1 (x2 )φ2 (x3 ) which cor-
respond to particles 1 and 2 in state 1 ≡ n1 and particle 3 in state 2 ≡ n2 , but we must
use instead the symmetrized wavefunction
r
1
Ψ= (φ1 (x1 )φ1 (x2 )φ2 (x3 ) + φ1 (x1 )φ2 (x2 )φ1 (x3 ) + φ2 (x1 )φ1 (x2 )φ1 (x3 )) .
3!
All we can say about this is that there are two particles in state |1i and one particle
in state |2i. Ψ is fully determined by the fact that φ1 is used twice and φ2 used once.
For spin 21 fermions we have
where α is “spin up” ↑ and β is spin down ↓ with H and En independent of α and
β. We can use determinants to build the antisymmetric wavefunctions.
For instance, given ψ1 (x, µ) and ψ2 (x, µ) (where 1 ≡ n1 , 2 ≡ n2 and µ = α or
β) we get the antisymmetrized version
r
1 ψ1 (x1 , µ1 ) ψ1 (x2 , µ2 )
Ψ(x1 , µ2 , x2 , µ2 ) = .
2! ψ2 (x1 , µ1 ) ψ2 (x2 , µ2 )
Ψ reflects the Pauli exclusion principle which forbids any two of the ψi or any two
sets (x, µ) from being the same.
Each Ψ is determined fully by the number of times each one particle wavefunction
is used in the product term that we (anti)symmetrize.
We see that the microstate |ii of S is fully determined by i ≡ {nr }. We obtain the
full set of microstates of S by letting the nr vary without restriction over their allowed
range of values. (Thus Ni and Ei cannot themselves be restricted — this is why we
use the grand ensemble method.)
We can now write down the grand partition function
X
Z= e−β(Ei −µNi )
i
X
= e−β(n1 1 +n2 2 +···−µn1 −µn2 −... )
n1 ,n2 ,...
YX
= e−βnr (r −µ) .
r nr
Y
Z= 1 + e−β(r −µ) . (3.10)
r
Now
X nr e−β(r −µ)
n¯r =
n1 ,n2 ,...
Z
1 ∂ log Z
=− s 6= r
β ∂r β,µ,s
1
= β( −µ) .
e r +1
th
P
We see that N = r n̄r . n̄r is the average occupation number of the r one
particle state at thermal equilibrium. This is the Fermi-Dirac distribution.
For bosons, 0 ≤ nr < ∞ and
Y 1
Z= −β(
.
1−e r −µ)
r
1
n̄r = . (3.11)
eβ(r −µ) −1
This is the Bose-Einstein distribution.
If there are gr one particle states of energy r we can write the average number of
particles with energy r as
gr
n̄(r ) = .
eβ(r −µ) ∓ 1
24 CHAPTER 3. GRAND ENSEMBLE METHODS
1
where g() is the density of states factor, DV 2 as in section 1.5.3, where D =
32
2π 2m
h2 gS and gS = 2S + 1 is the spin degeneracy.
The average number of particles with energy in the range → + d is
g()d
n()d = .
eβ(−µ) ∓ 1
Thus in the continuum limit, the grand partition function Z is given by
Z ∞
log Z = ∓ g() log(1 ∓ e−β(−µ) ) d.
0
We can now use the results of section 3.1 to find things like N and E,
∞ ∞
g() d g() d
Z Z
N= β(−µ)
E= .
0 e ∓1 0 eβ(−µ)∓1
1
In three dimensions, g() = DV 2 and so (integrating by parts) we see that
∞ 3
2 2
Z
log Z = DV β(−µ)
0 3e ∓1
2
= β.
3
1
Combining this with (3.9) we find that P V = 32 E. The 2
3 comes from the 2 factor
in g().
If ey 1 we can neglect the 1 in the denominator and find that n() ∝ e−β g().
We can approximate the integrals (expand the integrand) to get
eβµ
E ∼ 23 N kT 1 ∓ √ + . . . .
4 2
3.3. BLACK BODY RADIATION 25
3
√
π
In the lowest approximation E = 23 N kT and N = DV (kT ) 2 2 .
The condition e−βµ 1 is thus
32
2mπkT V
1 if gS = 1.
h2 N
NP 1
P V = N kT ∓ 3 √ .
(kT ) D 8π
2
1 X r
n̄r = and E = .
eβr − 1 r
eβr − 1
8πV 2
dE = ν dνkT = kT g(ν) dV,
c3
which agrees with the classical result of energy kT per normal mode of radiation.
This is the classical equipartition of energy. Using this result, dE 2
dν ∝ ν gives a diver-
gent energy, which is called the ultraviolet catastrophe.
Using the full formula for the energy we find that
26 CHAPTER 3. GRAND ENSEMBLE METHODS
∞
E 8π z 3 dz
Z
e= = (kT )4
V (hc)3 0 ez − 1
= σT 4 .
5 4
8π k
This is Stefan’s law, and σ = 15h 3 c3 is Stefan’s constant. We see that the energy
E
S = k log Z +
T
4E S 4 3
and we can evaluate k log Z = 3T . The entropy density V = 3 σT → 0 as
T → 0. The energy
43
4 3S 1 1
E = V σT = 1 ∝ V − 3 at constant entropy.
4 (V σ) 3
∂E 1E 1 4
The pressure P can now be calculated from P = − ∂V S
= 3V = 3 σT .
Finally the density of photons, n = N
V ∝ T 3
(see example sheet 3).
• electrons in solids,
√ 2m
32
where g() = DV , D = 4π h3 and
1
F () = .
eβ(−µ) +1
The range 0 ≤ e−βµ < ∞ is allowed without blowup of F . The region e−βµ 1
is the classical realm and we expect that quantum mechanical effects will be most
pronounced at low temperature, eβµ 1.
We assume that µ is finite and positive and µ = EF = kTF is constant at T = 0.
We further assume that µ = EF + O(kT ) for small T . It can be shown that µ =
EF + O(kT )2 .
3.4. DEGENERATE FERMI GAS 27
Now
(
β(−µ) 0 < EF
lim e =
T →0 ∞ > EF ,
so that
(
1 < EF
lim F () =
T →0 0 > EF .
3
N = DV 32 EF2 (3.12)
5
2 2 3
E = DV 3 EF = 5 N EF . (3.13)
Z ∞
N= g()F () d and
Z0 ∞
E= g()F () d.
0
We want to find C = ∂E ∂
∂T V
(which is proportional to the usual CV ). We take ∂T
of both of the above to find
∞
∂F
Z
C= g() ( − EF ) d.
0 ∂T
28 CHAPTER 3. GRAND ENSEMBLE METHODS
At low temperature ∂F∂T is very like a delta function and so the region ≈ EF
dominates the integral.
We approximate g() ≈ g(EF ) and µ ≈ EF . This gives us
∞
g(EF ) eβ(−EF )
Z
2
C∼ d( − EF ) 2 ( − EF )
kT 2 0 eβ(−EF ) +1
∞ 2 z
z e dz
Z
= g(EF )k 2 T 2.
−βEF (ez + 1)
π2 T
C∼ Nk ,
2 TF
where TF (the Fermi temperature) is defined by EF = kTF . This approximation
is expected to be good for T TF .
where
∞
X enβµ
f (−βµ) = 3 .
n=1 n2
fermions (which have the Pauli principle), but no law stops bosons from condensing
into the = 0 state if need be. We write N = N0 + NC , where N0 is the number of
particles in the = 0 state and NC is the number of particles in > 0 states. Then for
T > TB
N √
= D 2π f (−βµ).
V
N 3
For T = TB , V = D̂(kTB ) 2 , defining TB . For T < TB then
32
NC 3 NC T
= D̂(kT ) 2 , giving = .
V N TB
T ≈ Tsun = 107 K
M ≈ Msun , and
ρ ≈ 107 ρsun .
We regard them as being a mass of helium at T ≈ 107 K and under extreme com-
pression. For T ≈ 107 K, kT ≈ 103 eV is much greater than the binding energy of
electrons to helium, so that thermal collisions completely ionize all the atoms, produc-
ing an electron gas.
To a good approximation this may be viewed as a Fermi gas in the degenerate
(negligible T ) limit. This may be seen by computing TF , the natural temperature scale
of the problem (the Fermi temperature). Now
23
h2
3N
kTF = EF = ≈ 2 × 106 eV.
2m 8πV
11
Since N V is so large TF ≈ 10 K T .
The helium nuclei neutralise the charge of the star and produce the gravitational
attraction which counteracts the extreme zero-point pressure of the electron gas (which
dominates the zero-point pressure from the nuclei).
We can calculate the total energy E = Eelec (R) + Egrav (R) and find the radius R0
of the star by minimising this.
Treating the electrons relativistically we have
EF
N 8π
Z
1
= 3 3 d(2 − m2 c4 ) 2 .
V ~ c mc2
√ N
Let 2 − m2 c4 = mc2 x, so that the integral for V can be done to get
N 8π x3
= 3 3 (mc2 )3 F .
V ~ c 3
30 CHAPTER 3. GRAND ENSEMBLE METHODS
Z xF
E 8π p
= 3 3 (mc2 )4 x2 dx 1 + x2
V ~ c 0
and so E
N = 34 mc2 xF + x1F + O(x−2
F ) . We know that V ∝ R3 and so xF ∝
R−1 . Hence
a γ
E= + bR − ,
R R
where a, b and γ are positive constants. This only has a minimum if γ ≥ a, which
leads to the Chandrasekhar upper limit on the mass of a white dwarf.
Chapter 4
4.1 Introduction
Recall the result Z = z N for a system of distinguishable non-interacting particles. It
can be shown that in the classical limit
X X
z= e−βr = hr|e−β Ĥ |ri
r r
gives
Z
z = h−3 d3 p d3 q e−βH(p,q) , (4.1)
where Ĥ(p̂, q̂) is the quantum mechanical Hamiltonian and H(p, q) is the classical
Hamiltonian as a function of classical variables p and q.
The average for the system of a physical variable f (p, q) is
R 3 3
d p d q f (p, q)e−βH(p,q)
hf (p, q)i = R .
d3 p d3 q e−βH(p,q)
log z
We can see that hH(p, q)i = − ∂ ∂β agrees with the result
V
∂ log Z ∂ log z
E=− = −N .
∂β V ∂β V
Now
31
32 CHAPTER 4. CLASSICAL STATISTICAL MECHANICS
We want to write down the partition function Z = z N . To apply (4.1) we need the
Hamiltonian H. To find the Hamiltonian we first write down the Lagrangian
L = 21 mẋ2 + 12 I θ̇2 + sin2 θφ̇2 .
(V ≡ 0 in this rigid case.) Note that the Lagrangian splits neatly into translational
motion of G and rotational motion about the centre of mass.
We define the generalised momenta pα = ∂∂L q̇α :
Now
X p2 p2 p2φ
H= q̇α pα − L = + θ + ,
α
2m 2I 2I sin2 θ
and
1
Z
z= d2 p d3 q dpφ dφ dpθ dθ e−βH = zt zr ,
h5
where
32
1 2mπ
Z
3 3 − 12 mβp2
zt = 3 d pd qe =V
h βh2
and
p2
1 β
p2θ + sinφ = 8π2 IkT .
Z
− 2I 2θ
zr = 2 dpφ dφ dpθ dθ e
h h2
We evaluate the above integral by first doing the pθ , pφ and φ integrals and then
doing the θ integral.
23 8π2 IkT
Thus z = zt zr = V 2mπkT
h2 h2 . This gives E = 25 N kT .1
4.3 Paramagnetism
Each molecule of an N molecule solid acts as a little magnet fixed at its own lattice
site and free only to rotate about it. Each molecule has a dipole moment m and gives
1 Which ought to be expected!
4.4. SPECIFIC HEATS 33
N m2 B
For small y (high T ) we thus have Curie’s law, M = 31 N my = 3kT .
N
d3 pr d3 qr −βH
Z Y
Z= e
r=1
h3
3N
2πmkT 2 N
= V K
h2
= Z0 K,
where Z0 = z0N and z0 is the partition function for one molecule of a spinless gas
of N non-interacting molecules and
We suppose that λrs = e−βφ(Rrs ) − 1 is small (weak interaction) and we treat our
results to lowest non-trivial order.
Then
Z Y !
X
K = V −N d3 qr 1 + φ(Rrs )
r r<s
N (N − 1)
Z
=1+ d3 qa d3 qb λab (no summation).
2V 2
N 2 f (T )
defining f (T ). Then K = 1 + 2V (as N − 1 ∼ N ) and
N 2 f (T )
log Z = N log V + + stuff which does not depend on V .
V
∂ log Z
Using βP = ∂V we get
β
∞
N f (T )
Z
P V = N kT 1− with f (T ) = 4πy 2 dy e−βφ(y) − 1 . (4.3)
2V 0
If we take a specific φ we can recover the van der Waals’ equation of state (see page
15).
4.6. THE MAXWELL DISTRIBUTION 35
Stirling’s formula
We derive the approximation for Stirling’s formula from the Γ function using Laplace’s
method.
Recall that
Z ∞
Γ(z) = tz−1 e−t dt
0
Z ∞ Z ∞
n! = tn e−t dt = en log t−t dt.
0 0
t
Let v = n, so that
Z ∞
n! = nn+1 en(log v−v) dv.
0
, so
2
n −1− (v−1)
2
n(log v−v)
Now for large n, e ∼e
Z ∞
nu2 √
n! ∼ nn+1 e−n e− 2 du = 2πne−n nn .
−∞
37