Perturbation Theory of the Free Energy via the Mesoscopic Combined Partition Function

TL;DR

This paper develops a perturbation theory for the Helmholtz free energy of classical N-body systems within a mesoscopic framework, deriving formulas that recover known equations and quantify non-extensivity.

Contribution

It introduces a systematic perturbation approach for mesoscopic free energy, including mutual information corrections, and connects to classical equations like van der Waals.

Findings

Recovers van der Waals equation and Barker--Henderson result.

Provides a coupling-parameter integration formula for free energy.

Quantifies non-extensivity via mutual information corrections.

Abstract

We develop a systematic perturbation theory for the Helmholtz free energy of a classical $N$-body system within the mesoscopic framework of~\cite{OsanoMeso,OsanoExtensivity}. The combined coarse-graining operator $\mathcal{C}=\mathcal{C}_x\circ\mathcal{C}_p$ acting on single-particle phase space partitions it into product cells $C_{i,\alpha}=V_i\times\Pi_\alpha$ and generates a mesoscopic partition function $\mathcal{Z}_{\rm meso}(\lambda)$ whose reference level factorises by the multinomial theorem: $\mathcal{Z}_{\rm meso}^{(0)}=(Z_1^{(0)})^N$. Perturbation theory for $\mathcal{F}_{\rm meso}(\lambda)=-k_BT\ln\mathcal{Z}_{\rm meso}(\lambda)$ in the inter-cell perturbation $\mathcal{V}_{\rm meso}$ yields the mesoscopic Gibbs--Bogoliubov inequality and an exact coupling-parameter integration formula. The full free energy satisfies \begin{equation*} F(\lambda)=\mathcal{F}_{\rm meso}(\lambda)-k_BT\!\sum_{i<j}I(i,j;\lambda)+O\!\left(|\Lambda|\ell^{-d}e^{-2\ell/\xi}\right), \end{equation*} where the inter-cell mutual informations $I(i,j;\lambda)$ are the corrections identified in the extensivity analysis. The first-order theory recovers the van der Waals equation and the Barker--Henderson result; the second-order term converges to the structure-factor formula in the fine-cell limit. For long-range interactions, factorisation fails, and the mutual-information corrections quantify the resulting non-extensivity.