Dissociative Water Potential for Molecular Dynamics Simulations

Abstract

A new interatomic potential for dissociative water was developed for use in molecular dynamics simulations. The simulations use a multibody potential, with both pair and three-body terms, and the Wolf summation method for the long-range Coulomb interactions. A major feature in the potential is the change in the short-range O-H repulsive interaction as a function of temperature and/or pressure in order to reproduce the density-temperature curve between 273 K and 373 at 1 atm, as well as high-pressure data at various temperatures. Using only the change in this one parameter, the simulations also reproduce room-temperature properties of water, such as the structure, cohesive energy, diffusion constant, and vibrational spectrum, as well as the liquid-vapor coexistence curve. Although the water molecules could dissociate, no dissociation is observed at room temperature. However, behavior of the hydronium ion was studied by introduction of an extra H+ into a cluster of water molecules. Both Eigen and Zundel configurations, as well as more complex configurations, are observed in the migration of the hydronium.