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

TL;DR

This study introduces a new simulation-based method to accurately determine the melting points of various water models by observing ice Ih with a free surface, avoiding superheating artifacts common in traditional approaches.

Contribution

The paper presents a novel simulation technique that estimates ice melting points without superheating, validated across multiple water models with results aligning with established methods.

Findings

No superheating observed in free surface simulations.

Melting point estimates agree with free energy and interface simulations.

Method applicable to various water models.

Abstract

Molecular dynamic simulations were performed for ice Ih with a free surface. The simulations were carried out at several temperatures and each run lasted more than 7ns. 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 Ih with a free surface does not occur. That allows 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.