Nuclear quantum effects on glassy water under pressure: Vitrification and pressure-induced transformations.

Abstract

We perform classical molecular dynamics (MD) and path-integral MD (PIMD) simulations of H2O and D2O using the q-TIP4P/F model over a wide range of temperatures and pressures to study the nuclear quantum effects (NQEs) on (i) the vitrification of liquid water upon isobaric cooling at different pressures and (ii) pressure-induced transformations at constant temperature between low-density amorphous and high-density amorphous ice (LDA and HDA) and hexagonal ice Ih and HDA. Upon isobaric cooling, classical and quantum H2O and D2O vitrify into a continuum of intermediate amorphous ices (IA), with densities in-between those of LDA and HDA (depending on pressure). Importantly, the density of the IA varies considerably if NQEs are included (similar conclusions hold for ice Ih at all pressures studied). While the structure of the IA is not very sensitive to NQE, the geometry of the hydrogen-bond (HB) is. NQE leads to longer and less linear HB in LDA, HDA, and ice Ih than found in the classical case. Interestingly, the delocalization of the H/D atoms is non-negligible and identical in LDA, HDA, and ice Ih at all pressures studied. Our isothermal compression/decompression MD/PIMD simulations show that classical and quantum H2O and D2O all exhibit LDA-HDA and ice Ih-HDA transformations, consistent with experiments. The inclusion of NQE leads to a softer HB-network, which lowers slightly the LDA/ice Ih-to-HDA transformation pressures. Interestingly, the HB in HDA is longer and less linear than in LDA, which is counterintuitive given that HDA is ≈25% denser than LDA. Overall, our results show that, while classical computer simulations provide the correct qualitative phenomenology of ice and glassy water, NQEs are necessary for a quantitative description.