Beyond Boltzmann's H-theorem: Demonstration of the relaxation theorem for a non-monotonic approach to equilibrium

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Reid, James
J. Evans, Denis
Bernhardt, Debra
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2012
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Abstract

Relaxation of a system to equilibrium is as ubiquitous, essential, and as poorly quantified as any phenomena in physics. For over a century, the most precise description of relaxation has been Boltzmann's H-theorem, predicting that a uniform ideal gas will relax monotonically. Recently, the relaxation theorem has shown that the approach to equilibrium can be quantified in terms of the dissipation function first defined in the proof of the Evans-Searles fluctuation theorem. Here, we provide the first demonstration of the relaxation theorem through simulation of a simple fluid system that generates a non-monotonic relaxation to equilibrium.

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The Journal of Chemical Physics

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136

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Physical sciences

Thermodynamics and statistical physics

Condensed matter modelling and density functional theory

Chemical sciences

Chemical thermodynamics and energetics

Engineering

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