Hidden force opposing ice compression

TL;DR

This paper explains the unusual behavior of ice under pressure by analyzing the Coulomb repulsion between electron pairs, revealing how virtual and real bonds respond differently to compression, affecting ice's physical properties.

Contribution

It introduces a novel explanation for ice's anomalies under pressure based on electron pair repulsion and bond virtuality, supported by experiments and simulations.

Findings

Ice's low compressibility is due to virtual-bond compression and real-bond elongation.

Phonon modes stiffen or soften depending on bond type under pressure.

The cohesive energy loss influences phase transition temperatures.

Abstract

Coulomb repulsion between the unevenly-bound bonding and nonbonding electron pairs in the O:H-O hydrogen-bond is shown to originate the anomalies of ice under compression. Consistency between experimental observations, density functional theory and molecular dynamics calculations confirmed that the resultant force of the compression, the repulsion, and the recovery of electron-pair dislocations differentiates ice from other materials in response to pressure. The compression shortens and strengthens the longer-and-softer intermolecular O:H lone-pair virtual-bond; the repulsion pushes the bonding electron pair away from the H+/p and hence lengthens and weakens the intramolecular H-O real-bond. The virtual-bond compression and the real-bond elongation symmetrize the O:H-O as observed at ~60 GPa and result in the abnormally low compressibility of ice. The virtual-bond stretching phonons (< 400 cm-1) are thus stiffened and the real-bond stretching phonons (> 3000 cm-1) softened upon compression. The cohesive energy of the real-bond dominates and its loss lowers the critical temperature for the VIII-VII phase transition. The polarization of the lone electron pairs and the entrapment of the bonding electron pairs by compression expand the band gap consequently. Findings should form striking impact to understanding the physical anomalies of H2O.