Unraveling the coherent dynamic structure factor of liquid water at the mesoscale by molecular dynamics simulations

Abstract

We present an investigation by molecular dynamics (MD)-simulations of the coherent dynamic structure factor, S(Q, t) (Q: momentum transfer), of liquid water at the mesoscale (0.1 Å-1 ≤ Q ≤ Qmax) [Qmax ≈ 2 Å-1: Q-value of the first maximum of the static structure factor, S(Q), of water]. The simulation cell-large enough to address the collective properties at the mesoscale-is validated by direct comparison with recent results on the dynamic structure factor in the frequency domain obtained by neutron spectroscopy with polarization analysis [Arbe et al., Phys. Rev. Res. 2, 022015 (2020)]. We have not only focused on the acoustic excitations but also on the relaxational contributions to S(Q, t). The analysis of the MD-simulation results-including the self-and distinct contributions to the diffusive part of S(Q, t)-nicely explains why the relaxation process hardly depends on Q in the low Q-range (Q ≤ 0.4 Å-1) and how it crosses over to a diffusion-driven process at Q ≈ Qmax. Our simulations also give support to the main assumptions of the model used to fit the experimental data in the above mentioned paper. The application of such a model to the simulation S(Q, t) data delivers (i) results for the relaxation component of S(Q, t) in agreement with those obtained from neutron experiments and (ii) longitudinal and transverse hydrodynamic-like components with similar features than those identified in previous simulations of the longitudinal and transverse current spectra directly. On the other hand, in general, our MD-simulations results of S(Q, t) qualitatively agree with the viscoelastic transition framework habitually used to describe inelastic x-ray scattering results.