Nuclear Quantum Effects Largely Influence Molecular Dissociation and Proton Transfer in Liquid Water under an Electric Field.

Abstract

Proton transfer in liquid water controls acid-base chemistry, crucial enzyme reactions, and the functioning of fuel cells. Externally applied static electric fields in water are capable of dissociating molecules and transferring protons across the H-bond network. However, the impact of nuclear quantum effects (NQEs) on these fundamental field-induced phenomena has not yet been reported. By comparing state-of-the-art ab initio molecular dynamics (AIMD) and path integral AIMD simulations of water under electric fields, I show that quantum delocalization of the proton lowers the molecular ionization threshold to approximately one-third. Moreover, also the water behavior as a protonic semiconductor is considerably modified by the inclusion of NQEs. In fact, when the quantum nature of the nuclei is taken into account, the proton conductivity is ∼50% larger. This work proves that NQEs sizably affect the protolysis phenomenon and proton transfer in room-temperature liquid water.