Bridging continuum and statistical thermodynamics via equations of state and the density of states.
The connection between molecular force fields and equations of state (EoS) is typically established at the level of predicted quantities, e.g., by comparing simulation data and EoS data. In this paper we show how an EoS can be used to extract the density of states (Omega) of a system thus establishing a deeper connection between EoSs and statistical thermodynamics. We also show how such an EoS Omega can be used to aid molecular simulation methods designed to map out Omega (like the multicanonical approach). Central to the implementation of these ideas is the fact that the configurational Omega is related to thermodynamic properties accessible by an EoS via Boltzmann's equation. Sample calculations are presented for the Omega relevant to isothermal-isobaric and grand canonical ensemble simulations using the hard-sphere system and the Lennard-Jones system as model fluids, and the Carnahan-Starling EoS and a cubic EoS, respectively, as thermodynamic models.
School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, New York 14853-5201, USA.
Ivan D
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Gospodinov
Fernando A
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Escobedo