Work fluctuation theorems and free energy from kinetic theory

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.

References in corpus (7)

• Experimental Free Energy Surface Reconstruction From Single-Molecule Force Spectroscopy Using Jarzynski's Equality
• Comparison of far-from-equilibrium work relations
• Failure of the work-Hamiltonian connection for free energy calculations
• An illustrative example of the relationship between dissipation and relative entropy
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• Work, work fluctuations, and the work distribution in a thermal non-equilibrium steady state