The refractive index and electronic gap of water and ice increase with increasing pressure

Abstract

Determining the electronic and dielectric properties of water at high pressure and temperature is an essential prerequisite to understand the physical and chemical properties of aqueous environments under supercritical conditions, e.g. in the Earth interior. However optical measurements of compressed ice and water remain challenging and it has been common practice to assume that their band gap is inversely correlated to the measured refractive index, consistent with observations reported for hundreds of materials. Here we report ab initio molecular dynamics and electronic structure calculations showing that both the refractive index and the electronic gap of water and ice increase with pressure, at least up to 30 GPa. Subtle electronic effects, related to the nature of interband transitions and band edge localization under pressure, are responsible for this apparently anomalous behavior.