Venture into Water's No Man's Land: Structural Transformations of Solid H_{2}O under Rapid Compression and Decompression.

Abstract

Pressure-induced formation of amorphous ices and the low-density amorphous (LDA) to high-density amorphous (HDA) transition have been believed to occur kinetically below a crossover temperature (T_{c}) above which thermodynamically driven crystalline-crystalline (e.g., ice I_{h}-to-II) transitions and crystallization of HDA and LDA are dominant. Here we show compression-rate-dependent formation of a high-density noncrystalline (HDN) phase transformed from ice I_{c} above T_{c}, bypassing crystalline-crystalline transitions under rapid compression. Rapid decompression above T_{c} transforms HDN to a low-density noncrystalline (LDN) phase which crystallizes spontaneously into ice I_{c}, whereas slow decompression of HDN leads to direct crystallization. The results indicate the formation of HDA and the HDN-to-LDN transition above T_{c} are results of competition between (de)compression rate, energy barrier, and temperature. The crossover temperature is shown to have an exponential relationship with the threshold compression rate. The present results provide important insight into the dynamic property of the phase transitions in addition to the static study.