Nuclear quantum effects: Their relevance in neutron diffraction studies of liquid water

Abstract

Corrections for nuclear quantum effects (NQE) have been calculated for classical molecular dynamics (MD) simulation models of light (H2O), heavy (D2O) and ‘null’ [(H2O)0.64(D2O)0.36] water. New path integral molecular dynamics (PIMD) simulations have also been conducted for the same systems. NQEs have somewhat smaller influence on the O-D and D-D partial radial distribution functions of heavy water than on the O-H and H-H ones of light water. After correcting for NQEs the O-‘H’ bondlengths in light and heavy water have become different: the O-D ones are about 0.5% shorter than the O-H ones. Following NQE corrections, the total RDF of ‘null’ water does show hydrogen related features at the position of the intramolecular O-‘H’ peak. Based on a cross-check procedure involving the NQE-corrected total and partial radial distribution functions, it can be stated that concerning the structure of liquid water, the assumption that H and D are equal is valid to a very good approximation for intermolecular correlations. These findings are also supported by our path integral molecular dynamics simulations.