Quantum Statistical Mechanics - I

Till now whatever we studied in statistical mechanics, was by using classical laws of motion. Majority
of systems which we want to describe using statistical mechanics, are inherently quantum in nature, and
classical laws cannot be used to describe them. For example, a gas of free electrons should be described
using quantum mechanics.
The state of a quantum system can be described at any instant of time by its wave function Ψ, which is
a function of position (or momenta, depending on the representation) coordinates of all the particles,
and time. In general, it can be just be represented as a vector in the Hilbert space. |Ψ⟩ can also be written
as a linear combination of eigenfunctions of any Hermitian operator of the Hilbert space. We will write
% , the so-called energy eigenstates, given
it in terms of the eigenstates of the Hamiltonian of the system H
% |Φ! ⟩ = 𝐸! |Φ! ⟩. The state of the system can now be written as
by H

|Ψ⟩ = + 𝑐! |Φ! ⟩ ,
!

where 𝑐! is a complex quantity which can be time dependent and |Φ! ⟩ are the eigen states. The
% can be calculated as
expectation value of an observable A

% |Ψ⟩
⟨Ψ| A % |Φ# ⟩
∑!,# 𝑐! ∗ 𝑐# ⟨Φ! | A
〈𝐴〉 = =
⟨Ψ|Ψ⟩ ∑!,# 𝑐! 𝑐# ⟨Φ! |Φ# ⟩
∗

% |Φ# ⟩
∑!,# 𝑐! ∗ 𝑐# ⟨Φ! | A
〈𝐴〉 =
∑! 𝑐! 𝑐!
∗

where we have used the orthonormality of |Φ! ⟩. Since 𝑐! are time dependent, we can measure the time
average expectation value of 𝐴 as it is should be.

% |Φ# ⟩
∑!,# 𝑐! ∗ 𝑐# ⟨Φ! | A
〈𝐴〉 = (1)
∑! 𝑐! ∗ 𝑐!
% represents a measurable macrosocopic observable of a system in thermal equilibrium, the
If A
postulates of quantum statistical mechanics are actually postulates about the form of 𝑐! ∗ 𝑐# . We write
the postulates of quantum statistical mechanics as follows. It clearly says that

1. Postulate of Equal a Priori Probability

1 𝐸 < 𝐸! < 𝐸 + ∆𝐸
𝑐! ∗ 𝑐! = 7
0 𝑂𝑡ℎ𝑒𝑟𝑤𝑖𝑠𝑒

2. Postulate of Random phases

𝑐! ∗ 𝑐# = 0 (𝑖𝑓 𝑛 ≠ 𝑚)
All of the preceding discussion can also be reformulated in term of density operator, instead of quantum
states. A quantum system in a state |Ψ⟩ can be described by a density operator given by

𝜌I = |Ψ⟩ ⟨Ψ| ,

Provided |Ψ⟩ is normalized. For an unnormalized state we can write it as

|Ψ⟩ ⟨Ψ|
𝜌I =
𝑇𝑟[ |Ψ⟩ ⟨Ψ|]

where Tr[. . . ] represents trace over a complete set of states. The expectation value of an observable
can then be written as
〈𝐴〉 = 𝑇𝑟[ 𝜌I 𝐴M]

If one uses the energy eigenstates of the system to take the trace over states of the system, one gets
% |Φ! ⟩
〈𝐴〉 = +⟨Φ! | 𝜌I |Φ# ⟩ ⟨Φ# | A
!,#

% |Φ! ⟩ (2)
〈𝐴〉 = + 𝜌!# ⟨Φ# | A
!,#

Where 𝜌!# is called the density matrix. If we compare the equations (1) and (2), we can read
𝑐! ∗ 𝑐#
𝜌!# =
∑! 𝑐! ∗ 𝑐!
Or
𝑐! ∗ 𝑐!
𝜌!# = 𝛿!#
∑! 𝑐! ∗ 𝑐!

The average value of an observable can now be written as

% |Φ! ⟩
〈𝐴〉 = + 𝜌!! ⟨Φ! | A
!

% over an ensemble which consists of copies

The above relation represents an average of the observable A
of the system, in different microstates (quantum states) |Φ% ⟩, |Φ& ⟩, |Φ' ⟩, etc. The microstate (quantum
state) |Φ( ⟩ occurs with a probability 𝜌(( . Here 𝜌!# is an example of a mixed-state density matrix. Such
a density matrix cannot represent a single system in a particular quantum state. It represents a mixture,
or an ensemble of systems in different microstates, occurring with different probability.
Microcanonical ensemble

With the density matrix formulation discussed above, we are all set to describe various ensembles in
quantum statistical mechanics. Firstly, the counting of microstates, which was done by calculating the
area in phase-space in classical statistical mechanics, is done by counting the quantum states of the
system, labelled by suitable quantum numbers:

1 1
R 𝑑𝑝 𝑑𝑞 [. . ] ⟶ + [. . ]
𝑁 ! ℎ')
!

The density matrix for the microcanonical ensemble is given by

𝑐! ∗ 𝑐!
𝜌!! =
∑! 𝑐! ∗ 𝑐!
With the condition
1 𝐸 < 𝐸! < 𝐸 + ∆𝐸
𝑐! ∗ 𝑐! = 7
0 𝑂𝑡ℎ𝑒𝑟𝑤𝑖𝑠𝑒
All those 𝑐! ∗ 𝑐! are equal to 1 whose 𝐸! lies between 𝐸 and 𝐸 + ∆𝐸. The rest are zero. So, ∑! 𝑐! ∗ 𝑐! is
the number of microstates whose energy eigenvalue lies between 𝐸 and 𝐸 + ∆𝐸. Call it as Ω
1
𝜌!! = XΩ 𝐸 < 𝐸! < 𝐸 + ∆𝐸
0 𝑂𝑡ℎ𝑒𝑟𝑤𝑖𝑠𝑒

Canonical ensemble

Canonical ensemble can be formulated exactly as it was done in classical statistical mechanics, by
having a system and a much bigger heat-bath. Since none of the arguments used in our earlier
formulation, was specific to the classical nature of the system, the result can be directly adapted here.
The canonical density matrix can be written as
𝑒 *+,!
𝜌!! = 𝑤ℎ𝑒𝑟𝑒 𝑍 = + 𝑒 *+,!
𝑍
!

where 𝑍 is the canonical partition function. Off-diagonal elements of the density matrix are zero.
Ensemble average of an observable can be written as

1
% |Φ! ⟩
〈𝐴〉 = + 𝑒 *+,! ⟨Φ! | A
𝑍
!

Where |Φ! ⟩ are the eigen states of the Hamiltonian of the system.
Grand canonical ensemble

The density matrix in the grand canonical ensemble can be written, in general, as

𝑒 *+(," */ )" )
𝜌-- = 𝑤ℎ𝑒𝑟𝑒 𝑍2 = + 𝑒 *+(," */ )" )
𝑍2
-

where 𝜇 is the chemical potential, and 𝑍2 the grand partition function. How the microstates of the
system are defined, may depend on the specific problem at hand. We will look at it in more detail when
studying the quantum statistics of identical particles. Ensemble average of an observable can be written
as
1
% |Φ! ⟩
〈𝐴〉 = + 𝑒 *+(," */ )" ) ⟨Φ! | A
𝑍
-