Crucial role of fragmented and isolated defects in persistent relaxation of deeply supercooled water

Abstract

Properties of water have been well elucidated for temperatures above $\sim$230 K and yet mysteries remain in the deeply supercooled region. By performing extensive molecular dynamics simulations on this supercooled region, we find that structural and dynamical instabilities are hidden in the experimentally inaccessible region between 235 K and 150 K. We find a hitherto undiscovered fragmentation from 220 K to 190 K, which is the break-up of large clusters consisting of molecules with locally distorted tetrahedral structure into small pieces with one or two isolated defects. The fragmentation leads to considerable changes in the relaxation dynamics of water. We reveal a crucial role of specific three-coordinated defects in slow but persistent structural relaxation. The presence of relaxation due to these specific defects makes water glass transition temperature $T_{\mathrm{g}}$ (= 136 K) extremely low and explains why the $T_{\mathrm{g}}$ of water is $\sim$ 1/2 of the melting temperature Tm, much lower than the commonly obeyed 2/3 rule of $T_{\mathrm{g}}/T_{\mathrm{m}}$.

arXiv comment24 pages, 5 figures, and 15 pages and 6 figures in supplementary material

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