Ice Regelation: Hydrogen-bond extraordinary recoverability and water quasisolid-phase-boundary dispersivity.
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 ηx(T/ΘDx) whose Debye temperature ΘDx is proportional to its characteristic phonon frequency ωx according to Einstein's relationship. A superposition of the ηx(T/ΘDx) curves for the H-O bond (x=H, ωH~3200 cm(-1)) and the O:H nonbond (x=L, ωL~200 cm(-1), ΘDL=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 Tm(P) profile clarifies that the H-O bond energy EH determines the Tm with derivative of EH=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.
Institute of Coordination Bond Metrology and Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, China.|Institute of Nanosurface Science and Engineering, Shenzhen University, Shenzhen 518060, China.
Xi
X
Zhang
Key Laboratory of Low-dimensional Materials and Application Technology (MOE) and School of Materials Science and Engineering, Xiangtan University, Xiangtan, 411105, China.
Yongli
Y
Huang
Institute of Coordination Bond Metrology and Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, China.
Peng
P
Sun
Institute of Coordination Bond Metrology and Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, China.
Xinjuan
X
Liu
Key Laboratory of Low-dimensional Materials and Application Technology (MOE) and School of Materials Science and Engineering, Xiangtan University, Xiangtan, 411105, China.
Zengsheng
Z
Ma
Key Laboratory of Low-dimensional Materials and Application Technology (MOE) and School of Materials Science and Engineering, Xiangtan University, Xiangtan, 411105, China.
Yichun
Y
Zhou
State Key Laboratory of New Ceramics and Fine Processing, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, China.
Ji
J
Zhou
School of Materials Science, Jilin University, Changchun 130012, China.
Weitao
W
Zheng
NOVITAS, School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798.
Chang Q
CQ
Sun