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Direct calculation of solid-liquid coexistence points of a binary mixture by thermodynamic integration.

Apte PA, Kusaka I

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

We present a new thermodynamic integration method that directly connects the liquid and the solid phases of a binary mixture by a reversible path. The states along the path are simulated in the isothermal-isobaric semigrand canonical ensemble, in which temperature, pressure, the total number of particles, and the fugacity fractions of the components are held fixed. The thermodynamic integration yields the chemical-potential difference between the two phases for one of the components and this information is then used to locate the solid-liquid coexistence points. The melting temperatures predicted by our method agree well with those predicted by the Gibbs-Duhem integration for a truncated and shifted Lennard-Jones system with a cutoff radius of 2.5sigma.

Published 2 December 2005 in J Chem Phys, 123(19): 194503.
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