Abinitio Electronic Structure of Liquid Water.

Abstract

Self-consistent GW calculations with efficient vertex corrections are employed to determine the electronic structure of liquid water. Nuclear quantum effects are taken into account through abinitio path-integral molecular dynamics simulations. We reveal a sizable band-gap renormalization of up to 0.7eV due to hydrogen-bond quantum fluctuations. Our calculations lead to a band gap of 8.9eV, in accord with the experimental estimate. We further resolve the ambiguities in the band-edge positions of liquid water. The valence-band maximum and the conduction-band minimum are found at -9.4 and -0.5 eV with respect to the vacuum level, respectively.