Ice-water Interface: Correlation between Structure and Dynamics

TL;DR

This study investigates the relationship between structure and dynamics at the ice-water interface and other interfaces, revealing how properties deviate from bulk values and establishing correlations between structural order and molecular mobility.

Contribution

The paper introduces a new quantitative correlation between tetrahedrality and dynamics across various interfaces, enhancing understanding of interfacial behavior.

Findings

Water exchange at the ice-water interface occurs on ~10 ps timescale.

Structural deviations from bulk diminish beyond ~1 nm, but dynamical properties take longer to converge.

A strong correlation between tetrahedrality and diffusion is observed across all studied interfaces.

Abstract

To comprehend the complexities of the ice-water interface, we perform a study that attempts to correlate the altered dynamics of water to its perturbed structure at, and due to, the interface. The deviation from bulk values of structural and dynamical quantities at the interface are obtained by computer simulations. Water molecules are found to get exchanged between the ice-like and water-like domains of the interface with a time scale of the order of ~10 ps. To investigate the effect of interfaces in general, we study three other systems, namely (i) water between two hydrophobic nano-slabs, (ii) water at protein and (iii) DNA surfaces. In all these systems, we find that the difference from bulk properties become negligible beyond ~1 nm, with structural features converging to bulk values faster than the dynamical properties. Even in the case of the latter, we find that single-particle and collective properties behave differently. The approach to bulk values is rapid except for collective shell-dipole moments. We present a new insightful characterization of the surfaces by establishing a quantitative correlation between tetrahedrality order parameter (q_td) and dynamics by diffusion (D) and angular jumps. In the ice-water system, we find that the variation of qtd, as we move from solid to the liquid phase, correlated well with D. The correlation is found to be present in all the interfaces studied. Our results can be used to explain the experimental outcomes of the likes of dielectric relaxation and solvation dynamics.