Work fluctuation theorems and free energy from kinetic theory

TL;DR

This paper derives work fluctuation theorems from kinetic theory for a particle in a heat bath, discusses thermodynamic quantities, and compares theoretical predictions with particle simulations, revealing complex work distributions.

Contribution

It provides a kinetic theory derivation of work fluctuation theorems and analyzes their practical accuracy through simulations and experiments.

Findings

Work fluctuation relations are derived from the Boltzmann-Lorentz kinetic equation.

Simulations show work distributions are complex but relatively insensitive to interaction potentials.

The results validate the applicability of fluctuation theorems in kinetic theory contexts.

Abstract

The formulation of the First and Second Principles of thermodynamics for a particle in contact with a heat bath and submitted to an external force is analyzed, by means of the Boltzmann-Lorentz kinetic equation. The possible definitions of the thermodynamic quantities are discussed in the light of the H theorem verified by the distribution of the particle. The work fluctuation relations formulated by Bochkov and Kuzovlev, and by Jarzynski, respectively, are derived from the kinetic equation. In addition, particle simulations using both the direct simulation Monte Carlo method and Molecular Dynamics, are used to investigate the practical accuracy of the results. Work distributions are also measured, and they turn out to be rather complex. On the other hand, they seem to depend very little, if any, on the interaction potential between the intruder and the bath.