The free energy of expansion and contraction: Treatment of arbitrary systems using the Jarzynski equality

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Davie, Stuart
Reid, James
Bernhardt, Debra
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2012
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Thermodynamic integration, free energy perturbation, and slow change techniques have long been utilised in the calculation of free energy differences between two states of a system that has under- gone some transformation. With the introduction of the Jarzynski equality and the Crooks relation, new approaches are possible. This paper investigates an important phenomenon - systems under- going a change in volume/density - and derives both the Jarzynski equality and Crooks relation of such systems using a statistical mechanical approach. These results apply to systems with arbitrary particle interactions and densities. The application of this approach to the expansion/compression of particles confined within a vessel with a piston and within a periodic system is considered.

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The Journal of Chemical Physics

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136

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Physical sciences

Thermodynamics and statistical physics

Chemical sciences

Transport properties and non-equilibrium processes

Statistical mechanics in chemistry

Engineering

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