Nuclear quantum effects on the thermodynamic, structural, and dynamical properties of water

We perform path-integral molecular dynamics (PIMD) simulations of H₂O and D₂O using the q-TIP4P/F model. Simulations are performed at P = 1 bar and over a wide range of temperatures that include the equilibrium (T≥ 273 K) and supercooled (210 ≤T < 273 K) liquid states of water. The densities of both H₂O and D₂O calculated from PIMD simulations are in excellent agreement with experiments in the equilibrium and supercooled regimes. We also evaluate important thermodynamic response functions, specifically, the thermal expansion coefficient α_P(T), isothermal compressibility κ_T(T), isobaric heat capacity C_P(T), and static dielectric constant ε(T). While these properties are in excellent [α_P(T) and κ_T(T)] or semi-quantitative agreement [C_P(T) and ε(T)] with experiments in the equilibrium regime, they are increasingly underestimated upon further cooling. It follows that the inclusion of nuclear quantum effects in PIMD simulations of (q-TIP4P/F) water is not sufficient to reproduce the anomalous large fluctuations in density, entropy, and electric dipole moment characteristic of supercooled water. It has been hypothesized that water may exhibit a liquid-liquid critical point (LLCP) in the supercooled regime at P > 1 bar and that such a LLCP generates a maximum in C_P(T) and κ_T(T) at 1 bar. Consistent with this hypothesis and in particular, with experiments, we find a maximum in the κ_T(T) of q-TIP4P/F light and heavy water at T≈ 230-235 K. No maximum in C_P(T) could be detected down to T≥ 210 K. We also calculate the diffusion coefficient D(T) of H₂O and D₂O using the ring-polymer molecular dynamics (RPMD) technique and find that computer simulations are in remarkable good agreement with experiments at all temperatures studied. The results from RPMD/PIMD simulations are also compared with the corresponding results obtained from classical MD simulations of q-TIP4P/F water where atoms are represented by single interacting sites. Surprisingly, we find minor differences in most of the properties studied, with C_P(T), D(T), and structural properties being the only (expected) exceptions.