文章基本信息

标题：Ice Regelation: Hydrogen-bond extraordinary recoverability and water quasisolid-phase-boundary dispersivity
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作者：Xi Zhang ; Yongli Huang ; Peng Sun 等
期刊名称：Scientific Reports
电子版ISSN：2045-2322
出版年度：2015
卷号：5
期号：1
DOI：10.1038/srep13655
语种：English
出版社：Springer Nature
摘要：Regelation, i.e., ice melts under compression and freezes again when the pressure is relieved, remains puzzling since its discovery in 1850’s by Faraday. Here we show that hydrogen bond (O:H-O) cooperativity and its extraordinary recoverability resolve this anomaly. The H-O bond and the O:H nonbond possesses each a specific heat η _x(T/Θ_Dx) whose Debye temperature Θ_Dx is proportional to its characteristic phonon frequency ω_x according to Einstein’s relationship. A superposition of the η _x(T/Θ_Dx) curves for the H-O bond (x = H, ω_H ~ 3200 cm⁻¹) and the O:H nonbond (x = L, ω_L ~ 200 cm⁻¹, Θ_DL = 198 K) yields two intersecting temperatures that define the liquid/quasisolid/solid phase boundaries. Compression shortens the O:H nonbond and stiffens its phonon but does the opposite to the H-O bond through O-O Coulomb repulsion, which closes up the intersection temperatures and hence depress the melting temperature of quasisolid ice. Reproduction of the T_m(P) profile clarifies that the H-O bond energy E_H determines the T_m with derivative of E_H = 3.97 eV for bulk water and ice. Oxygen atom always finds bonding partners to retain its sp³-orbital hybridization once the O:H breaks, which ensures O:H-O bond recoverability to its original state once the pressure is relieved.