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Supersolidity of undercoordinated and hydrating water

Supersolidity of ice, which was proposed in 2013 and intensively verified since then [C. Q. Sun et al. , Density, Elasticity, and Stability Anomalies of Water Molecules with Fewer than Four Neighbors, J. Phys. Chem. Lett. , 2013, 4 , 2565-2570; C. Q. Sun et al. , Density and phonon-stiffness anomali...

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Published in:Physical chemistry chemical physics : PCCP 2018-12, Vol.2 (48), p.314-3119
Main Author: Sun, Chang Q
Format: Article
Language:English
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Summary:Supersolidity of ice, which was proposed in 2013 and intensively verified since then [C. Q. Sun et al. , Density, Elasticity, and Stability Anomalies of Water Molecules with Fewer than Four Neighbors, J. Phys. Chem. Lett. , 2013, 4 , 2565-2570; C. Q. Sun et al. , Density and phonon-stiffness anomalies of water and ice in the full temperature range, J. Phys. Chem. Lett. , 2013, 4 , 3238-3244], refers to the water molecules being polarized by molecular undercoordination, which is associated with the skin of bulk ice, nanobubbles, and nanodroplets (often called confinement), or by the electrostatic field of ions in salt solutions [X. Zhang et al. , Mediating relaxation and polarization of hydrogen-bonds in water by NaCl salting and heating, Phys. Chem. Chem. Phys. , 2014, 16 (45), 24666-24671; C. Q. Sun et al. , (H, Li)Br and LiOH solvation bonding dynamics: molecular nonbond interactions and solute extraordinary capabilities, J. Phys. Chem. B , 2018, 122 (3), 1228-1238]. From the perspective of hydrogen bond (O:H-O or HB with ":" representing the lone pairs on O 2− ) cooperative relaxation and polarization, this review features the recent progress and recommends future trends in understanding the bond-electron-phonon correlation in the supersolid phase. Supersolidity is characterized by a shorter and stiffer H-O bond, longer and softer O:H nonbond, deeper O 1s energy band, and longer photoelectron and phonon lifetimes. The supersolid phase is less dense, viscoelastic, and mechanically and thermally more stable. Furthermore, O:H-O bond cooperative relaxation offsets the boundaries of structural phases and increases the melting point while lowering the freezing temperature of ice, which is known as supercooling and superheating. Electrostatic polarization or molecular undercoordination endows the supersolidity by shortening and stiffening the H-O bond and lengthening and softening the O:H nonbond, deepening the O 1s energy level, and prolonging the photoelectron and phonon lifetime. The supersolid phase is less dense, viscoelastic, mechanically and thermally more stable, which offsets boundaries of structural phases and critical temperatures for phase transition of the coordination-resolved core-shell structured ice such as the 'no man's land' supercooling and superheating.
ISSN:1463-9076
1463-9084
1463-9084
DOI:10.1039/c8cp06115g