Thermodynamics of water clusters under high pressures. A case study for (H2O)(15) and (H2O)(15)CH4

Abstract

Thermal properties and structures of the water cluster containing fifteen molecules, either pure or doped with methane, are studied via classical parallel tempering Monte Carlo calculations in the isothermal–isobaric ensemble. The main emphasis is on structural transformations the cluster undergoes with increasing temperature and pressure. A simple TIP4P interaction model is employed for water and the unified-atom approximation with a Lennard-Jones potential is used to model the methane–water interaction. The results are compared with the data obtained recently for zero temperature via evolutionary algorithm calculations [Hartke, J. Chem. Phys., 2009, 130 art. no. 024905].