Mass-density and Phonon-frequency Relaxation Dynamics of Water and Ice at Cooling

TL;DR

This paper investigates how Coulomb repulsion and specific-heat disparities influence the relaxation dynamics of water and ice, explaining their density anomalies and phase transition behaviors through bond angle and length changes.

Contribution

It introduces a model linking Coulomb interactions and specific-heat differences to the relaxation dynamics and density anomalies of water and ice.

Findings

O:H-O bond relaxation explains water and ice density changes.

Master-slave role swapping causes volume expansion during freezing.

Bond stiffness variations correlate with phonon frequency shifts.

Abstract

Coulomb repulsion between the bonding electron pair in the H-O covalent bond (denoted by "-") and the nonbonding electron pair of O (":") and the specific-heat disparity between the O:H and the H-O segments of the entire hydrogen bond (O:H-O) are shown to determine the O:H-O bond angle-length-stiffness relaxation dynamics and the density anomalies of water and ice. The bonding part with relatively lower specific-heat is more easily activated by cooling, which serves as the "master" and contracts, while forcing the "slave" with higher specific-heat to elongate (via Coulomb repulsion) by different amounts. In the liquid and solid phases, the O:H van der Waals bond serves as the master and becomes significantly shorter and stiffer while the H-O bond becomes slightly longer and softer (phonon frequency is a measure of bond stiffness), resulting in an O:H-O cooling contraction and the seemingly "regular" process of cooling densification. In the water-ice transition phase, the master and the slave swap roles, thus resulting in an O:H-O elongation and volume expansion during freezing. In ice, the O--O distance is longer than it is in water, resulting in a lower density, so that ice floats.