Entropic Description of Gas Hydrate Ice-Liquid Equilibrium via Enhanced Sampling of Coexisting Phases

Phys Rev Lett. 2015 May 1;114(17):170601. doi: 10.1103/PhysRevLett.114.170601. Epub 2015 Apr 28.

Abstract

Metastable β ice holds small guest molecules in stable gas hydrates, so its solid-liquid equilibrium is of interest. However, aqueous crystal-liquid transitions are very difficult to simulate. A new molecular dynamics algorithm generates trajectories in a generalized NPT ensemble and equilibrates states of coexisting phases with a selectable enthalpy. With replicas spanning the range between β ice and liquid water, we find the statistical temperature from the enthalpy histograms and characterize the transition by the entropy, introducing a general computational procedure for first-order transitions.