Thermodynamic theory of equilibrium fluctuations

TL;DR

This paper extends classical thermodynamics to include equilibrium fluctuations by introducing new concepts like quasi-equilibrium states and a fluctuation postulate, enabling calculation of fluctuations in various systems.

Contribution

It develops a thermodynamic framework incorporating fluctuations, distinct from statistical mechanics, with a formalism applicable to diverse physical systems and interfaces.

Findings

Derived fluctuation relations for a simple fluid in multiple ensembles.

Analyzed fluctuations in finite-reservoir systems bridging canonical and micro-canonical ensembles.

Applied fluctuation theory to grain boundary properties and pre-melted interfaces.

Abstract

The postulational basis of classical thermodynamics has been expanded to incorporate equilibrium fluctuations. The main additional elements of the proposed thermodynamic theory are the concept of quasi-equilibrium states, a definition of non-equilibrium entropy, a fundamental equation of state in the entropy representation, and a fluctuation postulate describing the probability distribution of macroscopic parameters of an isolated system. Although these elements introduce a statistical component that does not exist in classical thermodynamics, the logical structure of the theory is different from that of statistical mechanics and represents an expanded version of thermodynamics. Based on this theory, we present a regular procedure for calculations of equilibrium fluctuations of extensive parameters, intensive parameters and densities in systems with any number of fluctuating parameters. The proposed fluctuation formalism is demonstrated by four applications: (1) derivation of the complete set of fluctuation relations for a simple fluid in three different ensembles; (2) fluctuations in finite-reservoir systems interpolating between the canonical and micro-canonical ensembles; (3) derivation of fluctuation relations for excess properties of grain boundaries in binary solid solutions, and (4) derivation of the grain boundary width distribution for pre-melted grain boundaries in alloys. The last two applications offer an efficient fluctuation-based approach to calculations of interface excess properties and extraction of the disjoining potential in pre-melted grain boundaries. Possible future extensions of the theory are outlined.