Chapter no 3: formulation of statistical methods

Assembly

Definition: the physical collection of systems being studied.

Definition: An assembly is an actual physical collection of many particles or subsystems.

This term is used to describe the real system with actual particles (atoms, molecules, etc.) interacting
and evolving in time.

Often used when talking about Bose-Einstein, Fermi-Dirac, or Maxwell-Boltzmann assemblies —

referring to the way particles are statistically distributed according to their quantum behavior.

Example: Ideal Gas in a Box

Imagine you have a box containing a gas of 1,000 identical particles at room temperature and fixed
volume.

 This is the actual gas in the box.

 It has real atoms bouncing around, colliding, exchanging energy.

 It exists in a single microstate at any instant, though it keeps changing over time.

 What you see in a lab: A gas with some macroscopic properties like pressure, volume,
temperature.

So, when we say "Maxwell-Boltzmann assembly", we’re talking about this collection of real gas
particles whose statistical behavior follows Maxwell-Boltzmann statistics.

Partition Function: A key mathematical quantity in many ensembles (especially the canonical ensemble)
is the partition function Z, which is the sum of the probabilities of all possible microstates of the system:

Z=∑e−βEi

This function is crucial because it allows us to calculate thermodynamic properties like free energy,
entropy, and heat capacity.

Comparison of System, Assembly & Ensemble

System: a large collection of microscopic particles (like atoms or molecules) whose collective behavior
we're trying to understand using statistical methods.

Assembly: definition: the physical collection of systems being studied.

Ensemble: definition: the virtual collection of systems being studied.

The term "assembly" is used more generally to describe the collection of systems, while "ensemble" is
used to refer to a mathematical construct for studying these systems.
Definition: In physics and especially in statistical mechanics, an ensemble is a large collection of virtual
copies of a system, considered all at once, where each copy represents a possible state, the system could
be in — according to certain physical conditions.

Imagine you're studying a gas in a box — but instead of just one box, you imagine infinitely many
identical boxes, each representing the gas with:

 the same macroscopic properties (like temperature, volume, number of particles), but

 possibly different microscopic arrangements (like positions and velocities of the particles)

 When you observe one physical system over a long time, you can (sometimes) gather enough
info about all its possible states — this is called the time average.
 But in statistical mechanics, it's hard to follow one system over time.
 So instead, we imagine an ensemble — many virtual copies of the system, each in a different
allowed state at the same moment.
 Then we calculate the ensemble average — the average over all these possible states.


examples:

1. Canonical Ensemble: It is the collection of a large number of essentially independent systems

having the same temperature (T), volume (V), and same number of particles (N).

The individual systems of canonical ensembles are separated by rigid, impermeable but
conducting walls.
As the separating walls are conducting, heat can be exchanged by the systems. As a result, all the
systems will arrive at a common temperature (T).
 You have a system: a box with a gas of N=1000N = 1000N=1000 particles.
 The box is in thermal contact with a heat reservoir (like a giant thermal bath).
 The temperature T, volume V, and number of particles N are all fixed.
 But the energy of the system is not fixed — it can fluctuate as heat is exchanged with the
reservoir.
 Instead of just this one gas box, you imagine infinitely many identical copies of it — a huge
number of boxes, each obeying the same macroscopic conditions (same T, N, V,).
 Each box is in a different microstate: the particles have different positions and velocities in each
copy.
 The collection of these boxes is called a canonical ensemble.

 System can exchange energy with a heat bath, but not particles.

 Energy fluctuates; temperature is fixed.

 − Ei
−Ei / K B T KB T
 Probability of a state with energy Ei: is the partition function
Pi=e Z
, where Z=∑ e Z

 Fixed Quantities are T, V, N

 Fluctuate: energy only

 Distribution: Boltzmann distribution

canonical partition function: The canonical partition function is defined as:

Z (T, V, N) =∑e−βEi

Where:

 β=1/kBT

 Ei is the energy of the ith microstate

 The sum runs over all possible microstates

For classical systems, this becomes an integral over phase space:

1
z (T ,V , N )= 3N
h N!
∫ e
−βH ( p, q )
d
3N
pd
3N
q

Use: from Canonical Partition Function Z we can compute

Helmholtz Free Energy(F=KBTlnZ), Average Energy (⟨ E ⟩ =

−∂lnZ
∂β
), Entropy(S=-
∂F
∂T V ( )
), Heat Capacity (

CV=
∂⟨E⟩
∂T
¿ & Pressure (for gases) (P=-
∂F
∂V ( )¿
T

EXAMPLE: find partition function and average energy.

 E0=0

 E1=ϵ=2 eV

 T=300 K

 β=1/kBT≈1/ (8.617×10−5⋅300) ≈38.7 eV−1

Now Compute Partition Function

Z (T, V, N) =∑e−βEi

⇒Z=e− β E +e− β E =1+e−(38.7)2=1+e−77.4≈1

0 1

Because e−77.4 is basically zero, we get:

Z≈1
Computing Average Energy we have

1 1
⟨ E ⟩ = ¿ E0 e− β E + E1 e−β E ¿= ( 0+ 2e−77.4 ) ≈ 0
0 1

z 1
Interpretation: At room temperature, the system almost never reaches the excited state. It stays in the
ground state.

2. Microcanonical Ensemble: it consists of large number of essentially independent system having same
energy, volume and same number of particles. The individual system of microcanonical ensemble is
separated by rigid, impermeable and well-insulated walls such that values of E, V, and N for a particular
system are not affected by the presence of other systems.

 Used for isolated systems (no exchange of energy or particles).

 All accessible states have the same energy and are equally probable.

 Entropy: S=kBlnΩ

 Fixed Quantities are E, V, N

 Fluctuate: nothing

 Distribution: Equal probability for all states

Partition Function of micro canonical ensemble:

In the microcanonical ensemble, the system is isolated, meaning it has a fixed energy (E), volume (V),
and number of particles (N). Unlike the canonical ensemble, where the partition function is a sum over
states weighted by e−βE, in the microcanonical ensemble, all accessible microstates with energy E are
considered equally probable. In this ensemble, the “partition function” is better known as the density of
states or the multiplicity function, denoted by:

Ω (E, V, N). This represents the number of microstates accessible to the system at exactly energy E.

1
ω ( E ,V ,N )= 3N
h N!
∫ 3N 3N
δ (H ¿ ¿( p , q)−E)d pd q ¿

3N 3N
2 2
V ( 2 πmE )
N
( 2 πmE )
Or ω ( E , V , N )= 3N
.
h N ! Γ( 3 N )
where ∫ d
3N
q=V
N
& ∫ δ( H −E)d 3 N p=
3N
¿
Γ( )
2 2
Where:

 H(p,q) is the Hamiltonian (total energy) of the system,

 δ is the Dirac delta function ensuring energy is exactly E,

 h is Planck's constant to make the expression dimensionless (important in statistical mechanics),

  N! accounts for indistinguishability of particles.

Use: The most direct use of the microcanonical partition function is to calculate the entropy:

S (E, V, N) =kBlnΩ

This is the fundamental thermodynamic quantity in the microcanonical ensemble.

It tells you the amount of disorder or the number of accessible microstates at energy E.

 Example: N=2

 V=1.0V

 h=6.626×10−34h

 m=4.65×10−26m

 E=1.0E

 N! =2

3N
 Γ( )=Γ (3) =2! =2
2
−26 −25
2 πmE =2⋅ π ⋅4.65 × 10 .1=2.922 ×10
3N
Now raise it to the power =3
2
3N
−74
and ( 2 πmE ) 2
=( 2.922 ×10 ) =2.50×10
−25 3

6
and h3 N =( 6.626 ×10−34 ) =8.92 ×10−119

and h3 N N !=8.92 ×10−119 ×2=1.784 × 10−198

3N
2
V N ( 2 πmE )
now ω ( E , V , N ) = .
h3 N N ! Γ ( 3 N )
2
2 −74
1 2.50 × 10
ω ( E , V , N )= −198
×
1.784 ×10 2

ω ( E , V , N )=7.01 ×10123

This is the number of microstates available to the system at energy E=1J.

2.Grand Canonical Ensemble: It is the collection of a large number of essentially independent
systems having the same temperature (T), volume (V), and chemical potential (μ). The individual systems
of grand canonical ensemble are separated by rigid, permeable and conducting walls.

 System can exchange both energy and particles with a reservoir.

 Described by T,V,μ
 Used to derive Fermi-Dirac and Bose-Einstein statistics.
 Fluctuate: Energy & particle number both

 Distribution: Fermi-Dirac / Bose-Einstein etc.

Partition Function of Grand Canonical Partition Function:

the grand partition function is defined as:

∞
Z (T,V,μ) = ∑ e− β (E− μN) Z N (T ,V )
N=0

∞
Z (T,V,μ) = ∑ e βμN Z N (T , V )
N=0

Where:

 β=1/kBT

 μ is the chemical potential

 ZN is the canonical partition function for N particles

It’s a weighted sum over all particle numbers N, where each term is the canonical partition function ZN,
weighted by the fugacity eβμN.

Q: Partition Function of micro canonical ensemble does not have simple form like canonical partition
function and Grand Canonical Ensemble?

Ans: “The microcanonical partition function does not have a simple form like the canonical and grand
canonical partition functions.”

Canonical and grand canonical ensembles involve exponential functions (easy to integrate)

Microcanonical involves delta functions (harder to work with)

The microcanonical partition function counts the number of microstates with exactly energy E
→ It involves a delta function: δ(H−E)

The canonical and grand canonical partition functions use an exponential weighting:
→ e−Eβ, which is smoother and easier to integrate or sum.
Partition Function in Statistical Mechanics:

The partition function is a mathematical function that encodes the statistical properties of a system in
thermodynamic equilibrium. It serves as the cornerstone of the canonical ensemble.