The exotic quasisolidity and supersolidity of water

The constant-temperature θ(t) thermal decay discriminates the performance of the quasisolid water from that of the saturated NaCl supersolid solution, unveiling the respective O:H–O bond relaxation dynamics. [Display omitted] •O:H–O bond specific-heats disparity entitles the quasisolidity of negativ...

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Veröffentlicht in:Coordination chemistry reviews 2024-10, Vol.517, p.216042, Article 216042
Hauptverfasser: Sun, Chang Q., Zhou, Yong, Fang, Hengxin, Wang, Sanmei, Huang, Yongli, Zhang, Xi, Ma, Zengsheng, Wang, Biao
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Sprache:eng
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Zusammenfassung:The constant-temperature θ(t) thermal decay discriminates the performance of the quasisolid water from that of the saturated NaCl supersolid solution, unveiling the respective O:H–O bond relaxation dynamics. [Display omitted] •O:H–O bond specific-heats disparity entitles the quasisolidity of negative thermal expansivity.•The H–O contracts ∼10 % in the supersolid phase owing to electrification and undercoordination.•Polarization drives the supersolid phase with the ωH shifting from 3200 to 3450 cm−1.•The viscoelastic, hydrophobic supersolid is less dense, more thermally diffusive, and stabler. This work features the recent findings of the quasisolid (QS, or quasi-liquid) in the temperature domain and supersolid due to electric polarization or molecular undercoordination, which are beyond the scope of the P-T phase diagram. The cooperativity of the coupling O:H–O bond in its segmental length, energy, specific heat, and associated polarization derive these abnormal phases. The specific-heat disparity defines structure phases varying from XI to Vapor and mass density evolution under ambient pressure. Possessing negative thermal expansivity (NTE), the QS phase transfers the liquid to the solid phase, which fosters ice buoyancy. The supersolid phase presents in the skin of water, ice, and droplets, and the ionic hydration cells and volumetric water with a current flow or under ∼106 eV/cm electric bias. The H–O bond of the supersolid phase is 8 ∼ 10 % shorter and vibrating at frequencies 7.3 % higher than that of the standard pristine water (0.1 nm in length and 3250 cm−1 in frequency). The supersolid has extraordinary elasticity, mechanical strength, optical reflectivity, structure order, thermal stability and diffusivity, catalytic capability, and chemical reactivity but 25 % lower mass density. The gel-like supersolidity endows ice and water with high hydrophobicity, viscoelasticity, catalytic and hydro-voltaic capability, and thermal diffusivity. The H–O bond contracts and absorbs energy during the Liquid-QS-Ice phase transition while doing contrastingly in the supersolid phase of the saturated NaCl solution under 254 K temperature.
ISSN:0010-8545
DOI:10.1016/j.ccr.2024.216042