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The physics behind water irregularity

物理 化学物理 极化率 凝聚态物理 热力学 结晶学 化学 分子 量子力学
作者
Chang Q. Sun,Yongli Huang,Xi Zhang,Zengsheng Ma,Biao Wang
出处
期刊:Physics Reports [Elsevier BV]
卷期号:998: 1-68 被引量:33
标识
DOI:10.1016/j.physrep.2022.11.001
摘要

The notion of asymmetrical Hydrogen Bond (O:H-O) Cooperativity and Polarizability (HBCP) has enabled exploration of the core physics behind irregularities of water and ice, particularly, the evolution of mass density, phase stability, energy exchange, and their transition velocity under perturbation. We humbly share the initiatives of the quasisolidity presented between Liquid and Ice, the supersolidity pertained to polarization by electrification or molecular undercoordination, and the H↔H and O:⇔:O repulsivity owing to the respective injection of excessive protons and lone pairs to the liquid by solvation. The O—O repulsivity forms the key that drives the O:H-O bond to cooperatively relax its segmental length, cohesive energy, vibration frequency, and specific heat upon perturbation, which establishes an efficient set of parameters to feature the bonding and electronic dynamics in the frequency–space–time domains. An interplay of the segmental specific heats defines the mass densities, phase boundaries, and the exotic quasisolid (QS) phase that exhibits negative thermal expansivity through H-O contracting less than the scale of O:H expansion upon cooling. However, the H-O bond undergoes cooling elongation in the Liquid and the Ice-I phase and remains silent in the XI phase. H-O bond absorbs energy by contraction and does it inverse at expansion. The O:H nonbond always relaxes more than the H-O bond does in contrasting direction. Mechanical compression symmetrizes the O:H-O segmental length associated with polarization, which disperses inwardly the QS phase boundary to lower the Tm for melting but raise the temperature TN for ice nucleation and the TV for evaporation, resulting in the phenomena of ice regelation and instant-ice formation. Polarization, however, has the contrast effect to compression on the hydrogen bond relaxation and phase transition. The polarization converts the pristine water into the gel-like, hydrophobic, and viscoelastic supersolid which is less-dense and thermally more diffusive and stable, entitling surface premelting, superheating at Tm, and supercooling at TN and TV. Polarization enhances the dielectrics of water and widens the bandgap of ice. The supersolidity ensures the 120 K superelasticity of ice microfibers and the 330 K stability of the electrified water bridge crossing the rims of infilled containers. The high elasticity of the softer O:H nonbond and the interface electrostatic repulsivity secure the slipperiness of ice and the superfluidity of water traveling in fine channels. The skin supersolidity and the O:H-O bond memorability uniquely foster the Mpemba effect — warm water cools more quickly. The H↔H or O:⇔:O repulsivity modifies the bonding network and solution properties through solvent H-O bond elongation, solute H-O bond contraction, and polarization. The HBCP premise has thus correlated the irregularity of water and ice to the O:H-O bonding and electronic dynamics under perturbation. Further extension of the HBCP to aqueous and molecular assemblies involved with electron lone pairs and coupling interactions could be even more fascinating and profoundly promising.
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