Characteristic state function
Particular relationship between the partition function of an ensemble
The characteristic state function or Massieu's potential in statistical mechanics refers to a particular relationship between the partition function of an ensemble .
In particular, if the partition function P satisfies
P = exp ( − β Q ) ⇔ Q = − 1 β ln ( P ) or P = exp ( + β Q ) ⇔ Q = 1 β ln ( P )
in which Q is a thermodynamic quantity, then Q is known as the "characteristic state function" of the ensemble corresponding to "P". Beta refers to the thermodynamic beta .
Examples
The microcanonical ensemble satisfies Ω ( U , V , N ) = e β T S hence, its characteristic state function is T S .
The canonical ensemble satisfies Z ( T , V , N ) = e − β A hence, its characteristic state function is the Helmholtz free energy A .
The grand canonical ensemble satisfies 𝒵 ( T , V , μ ) = e − β Φ , so its characteristic state function is the Grand potential Φ .
The isothermal-isobaric ensemble satisfies Δ ( N , T , P ) = e − β G so its characteristic function is the Gibbs free energy G .
State functions are those which tell about the equilibrium state of a system