Nuclear quantum effects and hydrogen bonding in liquids.

Abstract

We have employed ab initio path integral molecular dynamics simulations to investigate the role of nuclear quantum effects on the strength of hydrogen bonds in liquid hydrogen fluoride. Nuclear quantum effects are shown to be responsible for a stronger hydrogen bond and an enhanced dipole-dipole interaction, which lead, in turn, to a shortening of the H...F intrachain distance. The simulation results are analyzed in terms of the electronic density shifts with respect to a purely classical treatment of the nuclei. The observed enhanced hydrogen-bond interaction, which arises from a coupling of intra- and intermolecular effects, should be a general phenomenon occurring in all hydrogen-bonded systems.