Microcanonical and Canonical Ensembles
and the Partition Function
1 Microcanonical Ensemble
The microcanonical ensemble describes an isolated system with fixed:
• Energy (E),
• Volume (V ), and
• Number of particles (N ).
1.1 Microstates
A microstate is a specific configuration of the system’s particles. The total number of
accessible microstates is denoted by Ω(E, V, N ).
1.2 Entropy
The entropy is defined as:
S = kB ln Ω(E, V, N )
where kB is the Boltzmann constant. At equilibrium, all microstates are equally probable.
2 Canonical Ensemble
The canonical ensemble describes a system in thermal equilibrium with a heat reservoir
at temperature T .
2.1 Key Characteristics
• The system exchanges energy with the reservoir but not particles.
• Fixed quantities: temperature (T ), volume (V ), and number of particles (N ).
1
2.2 Boltzmann Distribution
The probability P (Ei ) of a microstate with energy Ei is given by:
e−βEi
P (Ei ) =
Z
where:
1 X
β= , Z= e−βEi
kB T i
3 Partition Function
The partition function Z is defined as:
X
Z= e−βEi
i
3.1 Thermodynamic Properties from Z
• Internal Energy (U ):
∂ ln Z
U = ⟨E⟩ = −
∂β
• Entropy (S): X
S = −kB P (Ei ) ln P (Ei )
i
• Helmholtz Free Energy (F ):
F = −kB T ln Z
• Heat Capacity (CV ):
∂U
CV =
∂T
4 Comparison: Microcanonical vs. Canonical En-
semble
Feature Microcanonical Ensemble Canonical Ensemble
System Type Isolated In thermal contact with a reservoir
Fixed Quantities E, V, N T, V, N
Key Quantity Ω(E, V, N ) Partition
P function Z
Entropy Formula S = kB ln Ω S = −kB i P (Ei ) ln P (Ei )
