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G Statistical Mechanics

Notes for Lecture

I THE GRAND CANONICAL ENSEMBLE

In the grand canonical ensemble the control variables are the chemical potential the volume V and the tem

perature T The total particle number N is therefore allowed to uctuate It is therefore related to the canonical

ensemble by a Legendre transformation with respect to the particle number N Its utility lies in the fact that it closely

represents the conditions under which experiments are often performed and as we shall see it gives direct access to

the equation of state

A Thermodynamics

In the canonical ensemble the Helmholtz free energy A N V T is a natural function of N V and T As usual we

perform a Legendre transformation to eliminate N in favor of A N

 N N A V T A N V T A N V T

A

N

V T

It turns out that the free energy A V T is the quantity P V We shall derive this result below in the context of

the partition function Thus

PV A N V T N

To motivate the fact that P V is the proper free energy of the grand canonical ensemble from thermodynamic

considerations we need to introduce a mathematical theorem known as Euler s theorem

Euler s Theorem Let f x x N be a function such that

f x x N n f

x x N

Then f is said to be a homo geneous function of degree n For example the function f x x is a homogeneous

function of degree f x y z xy z is a homogeneous function of degree however f x y e xy xy is not

a homogeneous function Euler s Theorem states that for a homogeneous function f

nf x x N

N

X

i

x

i

f

x i

Proof To prove Euler s theorem simply di erentiate the the homogeneity condition with respect to lambda

Then setting we have

which is exactly Euler s theorem

d

d

f x x N n f x x N

d

d

N

X

i

x

i

f

x i n n f x x N

N

X

i

x

i

f

x i

nf x x N

No w in thermodynamics extensive thermodynamic functions are homogeneous functions of degree Thus to see

how Euler s theorem applies in thermodynamics consider the familiar example of the Gibbs free energy

G G N P T

The extensive dependence of G is on N so being a homogeneous function of degree it should satisfy

G N P T G N P T

Applying Euler s theorem we thus have

or for a multicomponent system

But since

G

G N P T N N N

G X

j

j N j

G E TS PV

it can be seen that G N is consistent with the rst law of thermodynamics

Now for the Legendre transformed free energy in the grand canonical ensemble the thermodynamics are

d A dA dN N d P dV SdT N d

But since

 A A V T

d

A

A

V T d

the thermodynamics will be given by

V T dV

A

A

T

N

A

V T

P

V T

A

S

A

T

V

V

dT

Since A is a homogeneous function of degree and its extensive argument is V it should satisfy

Thus applying Euler s theorem

and since

A V T A V T

A

A V T V PV

V

A A N E TS N

the assignment A P V is consistent with the rst law of thermodynamics It is customary to work with P V

rather than P V so P V is the natural free energy in the grand canonical ensemble and unlike the other ensembles

it is not given a special name or symbol

B Partition function

Consider two canonical systems and with particle numbers N and N volumes V and V and at temperature

T The systems are in chemical contact meaning that they can exchange particles Furthermore we assume that

N N and V V so that system is a particle reservoir The total particle number and volume are

The total Hamiltonian H x N is

 V V V N N N

H x N H x N H x N

If the systems c ould not exchange particles then the canonical partition function for the whole system would be

where

Q

N V T

N h N Z dxe H x N H x N

N N

Q N V T Q N V T

N

Q

N V T

N h N Z dxe H x N

Q N V T

N h N Z dxe H x N

However N and N are not xed therefore in order to sum over all microstates we need to sum over all values that

N can take on sub ject to the constraint N N N Thus we can write the canonical partition function for the

whole system as

N

Q N V T f N N N N Q N V T Q N V T

X

N

N

where f N N is a function that weights each value of N for a given N Thus

f N is the number of con gurations with particles in V and N particles in V

f N is the number of con gurations with particles in V and N particles in V

etc

Determining the values of f N N amounts to a problem of counting the number of ways we can put N identical

f

N

f N N N N

f N N N N N

etc

or generally

f

N N

N

N

N N N N N

which is clearly a classical degeneracy factor If we were doing a purely classical treatment of the grand canonical

ensemble then this factor would appear in the sum for Q N V T however we always include the ad hoc quantum

correction N in the expression for the canonical partition function and we see that these quantum factors will

exactly cancel the classical degeneracy factor leading to the following expression

N

X

Q N V T Q N V T Q N V T

N

which expresses the fact that in reality the various con gurations are not distinguishable from each other and so

each one should count with equal weighting Now the distribution function x is given by

which is chosen so that

x N

h e H x N

N

Q N V T

Z dx x N

However recognizing that N N we can obtain the distribution for x N immediately by integrating over the

phase space of system

x N

Q N V T N h N

e H x N N h N Z dx e H x N

where the N h N prefactor has been introduced so that

N

Z dx x N

X

N

and amounts to the usual ad hoc quantum correction factor that must be multiplied by the distribution function for

each ensemble to account for the identical nature of the particles Thus we see that the distribution function becomes

x N Q N V T

Q N V T N h N

e

H x N

Recall that the Hemlholtz free energy is given by

Thus

Q

N V T e

A ln Q

A N V T

Q N V T e A N V T e A N N V V T

or

Q N V T

Q N V T

e A N N V V T A N V T

But since N N and V V we may expand

A

A

A N N V V T A N V T N N V V

A N V T N PV

Therefore the distribution function becomes

x N

h N

N

e

N e PV e H x N

h N

N

e

PV

e

N e H x N

Dropping the subscript we have

x N

We require that x N be normalized

e PV

X

N

e PV

N

h N e N e H x N

Z dx x N

X

N

N h N e N Z dxe H x N

Now we de ne the grand canonical partition function

Z V T

X

N

N h N e N Z dxe H x N

Then the normalization condition clearly requires that

Z

ln Z

V T

V T

e PV

PV

kT

Therefore P V is the free energy of the grand canonical ensemble and the entropy S V T is given by

S V T PV V k ln Z V T k ln Z V T V

T

We now introduce the fugacity de ned to be

e

Then the grand canonical partition function can be written as

Z

V T

X

N

N h N N Z dxe H x N

X

N

N Q N V T

which allows us to view the grand canonical partition function as a function of the thermodynamic variables V

and T

Energy

E hH x N i

Z

X

N

N

N Z dxH x N e H x N

N h

ln Z V T

V

Average particle number

hN i kT ln Z V T

V T

This can also be expressed using the fugacity by noting that

Thus

hNi ln Z V T

C Ideal gas

Recall the canonical partition function expression for the ideal gas

De ne the thermal wavelength as

Q N V T

N h

V m

h

m

N

which has a quantum mechanical meaning as the width of the free particle distribution function Here it serves as a

useful parameter since the canonical partition can be expressed as

Q N V T

N

V

N

The grand canonical partition function follows directly from Q N V T

Thus the free energy is

Z

V T

X

N

N V

N

PV

kT

ln Z

V

e V

In order to obtain the equation of state we rst compute the average particle number hN i

hNi ln Z

V

Thus eliminating in favor of hN i in the equation of state gives

P V hN ikT

as expected Similarly the average energy is given by

V

E ln Z V

hN ikT

where the fugacity has been eliminated in favor of the average particle number Finally the entropy

S V T k ln Z V T k ln Z V T hN ik hN ik ln V

V

hNi

which is the Sackur Tetrode equation derived in the context of the canonical and microcanonical ensembles

D Particle number uctuations

In the grand canonical ensemble the particle number N is not constant It is therefore instructive to calculate

the uctuation in this quantity As usual this is de ned to be

Note that

N p hN i hNi

Thus

ln Z V T N N Q N V T N N Q N V T

Z

X

N

Z

X

N

hN i hNi

N ln Z V T kT

ln Z V T kT V P

In order to calculate this derivative it is useful to introduce the Helmholtz free energy per particle de ned as follows

a v T N A N V T

where v V N is the volume per particle

The chemical potential is de ned by

A

N a v T N

a v T v

a

v

a v

v N

Similarly the pressure is given by

P V N a

A

v

a

v V v

 Also v Therefore P P v v and P P v v

v

a

v

a a

v

v v

v

a

v

v

v

v P v

But recall the de nition of the isothermal compressibility

Thus

and

V

T

V P v p v

P

v T

N r hN ikT T

v

and the relative uctuation is given by

N hNi r hN ikT T

N

v

p hNi ashN i

Therefore in the thermodynamic limit the particle number uctuations vanish and the grand canonical ensemble is

equivalent to the canonical ensemble