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The characteristic state function or Massieu's potentialcite-ref-1[1] 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 β Q ) ⇔ ⇔ Q = − − 1 β β ln ⁡ ⁡ ( P ) {\displaystyle P=\exp(-\beta Q)\Leftrightarrow Q=-{\frac {1}{\beta }}\ln(P)} or P = exp ⁡ ⁡ ( + β β Q ) ⇔ ⇔ Q = 1 β β ln ⁡ ⁡ ( P ) {\displaystyle P=\exp(+\beta Q)\Leftrightarrow Q={\frac {1}{\beta }}\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

• References

• The microcanonical ensemble satisfies Ω Ω ( U , V , N ) = e β β T S {\displaystyle \Omega (U,V,N)=e^{\beta TS}\;\,} hence, its characteristic state function is T S {\displaystyle TS} .

• The canonical ensemble satisfies Z ( T , V , N ) = e − − β β A {\displaystyle Z(T,V,N)=e^{-\beta A}\,\;} hence, its characteristic state function is the Helmholtz free energy A {\displaystyle A} .

• The grand canonical ensemble satisfies Z ( T , V , μ μ ) = e − − β β Φ Φ {\displaystyle {\mathcal {Z}}(T,V,\mu )=e^{-\beta \Phi }\,\;} , so its characteristic state function is the Grand potential Φ Φ {\displaystyle \Phi } .

• The isothermal-isobaric ensemble satisfies Δ Δ ( N , T , P ) = e − − β β G {\displaystyle \Delta (N,T,P)=e^{-\beta G}\;\,} so its characteristic function is the Gibbs free energy G {\displaystyle G} .

State functions are those which tell about the equilibrium state of a system

cite-note-11. ↑ citerefbalian2017Balian, Roger (2017-11-01). "François Massieu and the thermodynamic potentials". Comptes Rendus Physique. 18 (9–10): 526–530. Bibcode:2017CRPhy..18..526B. doi:10.1016/j.crhy.2017.09.011. ISSN 1631-0705. "Massieu's potentials [...] are directly recovered as logarithms of partition functions."