Absence of superheating for ice I_h with a free surface: a new method of determining the melting point of different water models

Abstract

Molecular dynamic simulations were performed for ice I_h with a free surface. The simulations were carried out at several temperatures and each run lasted more than 7 ns. At high temperatures the ice melts. It is demonstrated that the melting process starts at the surface and propagates to the bulk of the ice block. Already at the temperatures below the melting point, we observe a thin liquid layer at the ice surface, but the block of ice remains stable along the run. As soon as the temperature reaches the melting point the entire ice block melts. Our results demonstrate that, unlike in the case of conventional simulations in the NpT ensemble, overheating of the ice I_h with a free surface does not occur. This allows one to estimate the melting point of ice at zero pressure. We applied the method to the following models of water: SPC/E, TIP4P, TIP4P/Ew, TIP4P/Ice and TIP4P/2005, and found good agreement between the melting temperatures obtained by this procedure and the values obtained either from free energy calculations or from direct simulations of the ice–water interface.

Acknowledgements

It is a pleasure to acknowledge helpful discussions with Professor J. L. F. Abascal, Dr L. G. MacDowell, Dr E. Sanz, Dr C. McBride and R. G. Fernandez. This project has been financed by the grant FIS2004-06227-C02-02 of Direccion General de Investigacion, by the project S-0505/ESP/0299 of the Comunidad de Madrid and by the European Community under the grant No. MTDK-CT-2004-509249. One of us (CV) would like to thank the group of Molecular Modeling at the University of Lublin, and specially Andrzej Patrykiejew and Stefan Sokolowski for the hospitality during his stay in Lublin.