Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
The two systems are in thermal equilibrium at temperature T and chemical potential .
We assume that the system A2 is much larger than the system A1 , i.e., that
E2 >> E1 ,
N2 >> N1 ,
with
N1 + N2 = N = const
and
E1 + E2 = E = const,
where N and E are the particle number and the energy of the total system A = A1 + A2 .
The total Hamiltonian is defined as the sum of the Hamiltonians of A1 and A2 :
121
122 CHAPTER 10. GRAND CANONICAL ENSEMBLE
For the above assumption to be valid, we neglect interactions among particles in A1 and
A2 :
H12 = 0.
Since the total system A is isolated, its distribution function is given in the microcanonical
ensemble as
1
(q, p) = (E H1 H2 ),
(E, N )
with Z
(E, N ) = d3N q d3N p (E H1 H2 ).
We are now interested in the system A1 . As we did in the canonical ensemble, we integrate
the total probability density (q, p) over the phase space of the reservoir A2 :
Z
1 (q(1), p(1), N1 ) = d2 (q, p)
R
d2 (E H1 H2 , N ) 2 (E H1 , N N1 )
= = .
(E, N ) (E, N )
Since E1 << E and N1 << N , we can approximate the slowly varying logarithm of
2 (E2 , N2 ) around E2 = E and N2 = N and thus obtain:
S2 (E E1 , N N1 ) = kB ln 2 (E E1 , N N1 )
S2 S2
= S2 (E, N ) E1 N1 .
E2 N2 N2
E2 = E E2
E2 = E
N2 = N N2 = N
and
S2
= ,
N2 N2 = N T
E2 = E
E1
S2 (E E1 , N N1 ) = S2 (E, N ) + N1 + . . .
T T
The probability distribution function is then
The constant of proportionality is given by the grand canonical partition function Z(T, V ),
which normalizes the distribution function to 1:
Z
X d3N1 q(1) d3N1 p(1) H1 (q(1),p(1),N 1 )N1
Z= 3N 1N !
e kB T
.
N =0
h 1
1
1 1 H1 (q(1),p(1),N 1 )N1
1 (q(1), p(1), N1 ) = e kB T
h3N1 N1 ! Z
so that Z
X
d3N1 q(1) d3N1 p(1) 1 (q(1), p(1), N1 ) = 1
N1 =0
holds indeed.
After this derivation we can proceed without carrying the index (1). We only have to
keep in mind that we are describing a system in contact with a reservoir, where heat and
particles exchange is allowed.
10.2 Fugacity
By using the definition of the partition function in the canonical ensemble,
1
Z
ZN = 3N d3N q d3N p eH ,
h N!
we can rewrite the partition function in the grand canonical ensemble as
X
X
N
Z(T, ) = e ZN (T ) = z N ZN (T ) , (10.1)
N =0 N =0
where z = e/kB T is denoted as the fugacity. Equation (10.1) shows that Z(T, ) is the
discrete Laplace transform of ZN (T ). Obviously,
N
X z N ZN (T ) X e kB T ZN (T )
= = 1.
N =0
Z(T, ) N =0
Z(T, )
We define N
e kB T ZN (T )
wN =
Z(T, )
as the probability that the system at temperature T and with chemical potential contains
N particles.
124 CHAPTER 10. GRAND CANONICAL ENSEMBLE
From the average particle number < N >, we can calculate the chemical potential
where we used the definition of Z and the same procedure as the one we followed for the
canonical ensemble.
(T, V, ) = F (T, V, N ) N ; = P V.
10.4. GRAND CANONICAL POTENTIAL 125
Dont confuse the grand canonical potential (T, V, ) with the density of mi-
crostates (E)!!!
(T, V, ) = kB T ln Z(T, V, )
Z = e
CV = kB 2 (H < H >)2 0.
< N >= ln Z.
We consider now the second derivative of ln Z with respect to the chemical potential:
2
2 1 2
1
ln Z = Z + Z
2 Z 2 Z 2
= 2 < N >2 + 2 < N 2 >
2
2 1 2 1
<N ><N > = 2 ln Z = <N > .
2 T,V T,V
Proof :
We use the chain rule:
<N > V <N >
=
T,V
T,<N > V T,
V P <N >
= . (10.5)
P T,<N > T,<N > V T,
10.5. PARTICLE FLUCTUATIONS 127
P P
Note that P = P (T, ) and therefore
=
T,<N > T,V
The particle number and pressure can be obtained as derivatives of the grand canon-
ical potential:
<N > = ,
T,V
P = .
V T,
2 2
= ,
V V
we get the Maxwell relation:
<N > P
= . (10.6)
V T, T,V
V
= T V,
P T,<N >
P kB T <N >
= ln Z = .
T,V V T,V V
Then,
<N > T
= < N >2
T,V V
T h(N < N >)2 i
= 0.
V < N >2
The thermal compressibility is a measure of the particle number fluctuations.
For macroscopic systems, the particle fluctuations are negligible: for N >> 1, almost
all system copies in the grand canonical ensemble have the same particle number <
N >. Therefore, we have statistical equivalence between the grand canonical and the
canonical ensembles. Out of these considerations together with the energy fluctuations
considerations that we had in chapter 9, we conclude that for macroscopic systems the
three ensembles are equivalent.
128 CHAPTER 10. GRAND CANONICAL ENSEMBLE
1 - Calculate the grand canonical partition function out of the partition function in the
canonical ensemble, which we found in chapter 9 to be equal to
N
1 V
ZN (T, V, N ) = .
N ! 3T
V
Z1 (T, V, 1) = ,
3T
h
T = ,
2 m kB T
X N
Z = e kB T ZN (T )
N =0
N N
X N 1 V X 1 /kB T V /kB T V
= e kB T
= e = exp e .
N =0
N! 3T N =0
N! 3T 3T
V
(T, V, ) = kB T ln Z(T, V, ) = kB T e/kB T .
3T
3T
e/kB T = N ,
V
N 3T 1
P = kB T 3,
V T
10.6. EXAMPLE: IDEAL GAS IN THE GRAND CANONICAL ENSEMBLE 129
V P = kB T N equation of state,
and
3T V N 3T
5
S=N kB ln .
V 3T 2 V
V 5
S = kB N ln + Sackur-Tetrode equation.
N 3T 2
Summary ensembles
d3N q d3N p H
Z
Canonical ZN (T, V ) = e F (T, V, N ) = kB T ln ZN (T, V )
h3NZ N!
1
ensemble = 3N dE (E) eH ZN = eF
h N! 0
eN ZN (T )
P
Grand canonical Z(T, ) = N =0 (T, V, ) = kB T ln Z(T, V, )
PV
ensemble Z = e = e kB T