A First and Second Law for Nonequilibrium Thermodynamics: Maximum Entropy Derivation of the Fluctuation-Dissipation Theorem and Entropy Production Functionals

TL;DR

This paper develops a maximum entropy-based theoretical framework for nonequilibrium thermodynamics, deriving fluctuation-dissipation relations and entropy production functionals without relying on steady-state assumptions.

Contribution

It introduces a novel maximum entropy approach to derive a comprehensive, time-dependent description of nonequilibrium systems, connecting fluctuation theorems and thermodynamic laws.

Findings

Derivation of path probability of Onsager-Machlup form.

Introduction of path free energy and entropy functionals.

Proof of a microscopic form of the Clausius statement.

Abstract

A theory for non-equilibrium systems is derived from a maximum entropy approach similar in spirit to the equilibrium theory given by Gibbs. Requiring Hamilton's principle of stationary action to be satisfied on average during a trajectory, we add constraints on the transition probability distribution which lead to a path probability of the Onsager-Machlup form. Additional constraints derived from energy and momentum conservation laws then introduce heat exchange and external driving forces into the system, with Lagrange multipliers related to the temperature and pressure of an external thermostatic system. The result is a fully time-dependent, non-local description of a nonequilibrium ensemble. Detailed accounting of the energy exchange and the change in information entropy of the central system then provides a description of the entropy production which is not dependent on the specification or existence of a steady-state or on any definition of thermostatic variables for the central system. These results are connected to the literature by showing a method for path re-weighting, creation of arbitrary fluctuation theorems, and by providing a simple derivation of Jarzynski relations referencing a steady-state. In addition, we identify path free energy and entropy (caliber) functionals which generate a first law of nonequilibrium thermodynamics by relating changes in the driving forces to changes in path averages. Analogous to the Gibbs relations, the variations in the path averages yield fluctuation-dissipation theorems. The thermodynamic entropy production can also be stated in terms of the caliber functional, resulting in a simple proof of our microscopic form for the Clausius statement. We find that the maximum entropy route provides a clear derivation of the path free energy functional, path-integral, Langevin, Brownian, and Fokker-Planck statements of nonequilibrium processes.