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Direct calculation of solid-vapor coexistence points by thermodynamic integration: application to single component and binary systems.

Apte PA, Kusaka I

The Koffolt Laboratories, The Department of Chemical and Biomolecular Engineering, The Ohio State University, Columbus, Ohio 43210, USA.

We present a new thermodynamic integration method that directly connects the vapor and solid phases by a reversible path. The thermodynamic integration in the isothermal-isobaric ensemble yields the Gibbs free energy difference between the two phases, from which the sublimation temperature can be easily calculated. The method extends to the binary mixture without any modification to the integration path simply by employing the isothermal-isobaric semigrand ensemble. The thermodynamic integration, in this case, yields the chemical potential difference between the solid and vapor phases for one of the components, from which the binary sublimation temperature can be calculated. The coexistence temperatures predicted by our method agree well with those in the literature for single component and binary Lennard-Jones systems.

Published 19 May 2006 in J Chem Phys, 124(18): 184106.
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