Statistical Mechanics Cheat Sheet

May 2022

Introduction
0.1 Definitions 0.3 Potentials from partition
The first definition comes from the idea of that we can insulate a system from
all external influences so that no energy or particles are exchanged between
the system and the rest of the universe. The special insulator that achieves
this is called an adiabatic wall, and a system which is enclosed in adiabatic
walls is called an isolated system. Two systems separated by adiabatic
walls will not interact with each other. Conversely, if two systems are allowed
to remain in thermal contact and hence exchange thermal energy but not
exchange particles, they are said to be separated by diathermal walls. The
second definition is that of equilibrium – an isolated system left alone for some
(usually long) time will relax to a state where there is no macroscopic changes.
This end state is called the equilibrium state.
The Zeroth Law states that if systems A and B are in equilibrium with
C, then they are also in equilibrium with each other. The First Law is
a statement of conservation of energy, the change in energy ∆E is due to
work W down on the system and Q is the energy transferred into the system:
∆E = W + Q, dE = δW + δQ. The Second Law states that entropy tends
to increase: ∆ ≥ 0 for thermally isolated systems, equivalently dS = δQ T
for
reversible processes.

0.4 Maxwell Relations

       
∂P ∂S ∂T ∂P
= =−
∂T V ∂V T ∂V S ∂S V

The Helmoltz Free Energy, F = E − T S measures the capacity for the system
to do work at a fixed temperature. The Gibbs Free Energy, Φ = E − T S + P V .
       
∂S ∂V ∂V ∂T
Enthalpy H = E + P V , ∆HP = T ∆S = ∆Q, the enthalpy measures roughly =− =
∂P T ∂T P ∂S P ∂P S
the internal energy plus the work required to make space for it. A system wants
to evolve towards a state of higher entropy, it also wants to evolve towards a
state of lower F . The heat capacity
0.5 Other Formulas
 is defined
 by the change in energy due
to a change in temperature: CV = dδQ dT
at constant volume and similarly X X
V ⟨E⟩ = En ⟨Nn ⟩ , ⟨N ⟩ ⟨Nn ⟩
for constant pressure. The chemical potential is the change in internal n n
∂E
energy to create or destroy a single particle of species i: µi = ( ∂N )S,V . The  
i P ∂Ψ X
grand canonical potential or Landau potential is defined as Ψ = F − i µi Ni . Ψ(T, V, µ) = V =F − µi Ni
(T, S), (P, V ), (µ, N ) are conjugate pairs of variables, with the first of each ∂V T,µ i
pair an intensive variable and the second an extensive variable. An ensemble E = T S − P V + µN F = E − TS
is the space of all possible microstates consistent with some constraints. A
Ψ(T, V, µ) = −P (T, µ)V
microstate is a point in the system’s dynamical phase space. A function
of state is a thermodynamic quantity that is an exact function of its state
variables.

0.2 Thermodynamic potentials

       
∂F ∂E ∂F ∂Φ
P =− P =− S=− S=−
∂V T ∂V S ∂T V ∂T P
       
∂H ∂E ∂Φ ∂H
T = T = V = V =
∂S P ∂S V ∂P T ∂P S

P is pressure, E is internal energy, H is enthalpy, S is entropy, F is the free

energy, Φ is the Gibbs free energy, V is the volume, T is the temperature.
0.6 Cluster expansion

0.7 Formulas