Kumar Pradeep, Franzese Giancarlo, Stanley H Eugene
Center for Polymer Studies and Department of Physics, Boston University, Boston, Massachusetts 02215, USA.
Phys Rev Lett. 2008 Mar 14;100(10):105701. doi: 10.1103/PhysRevLett.100.105701. Epub 2008 Mar 11.
Using Monte Carlo simulations and mean field calculations for a cell model of water we find a dynamic crossover in the orientational correlation time tau from non-Arrhenius behavior at high temperatures to Arrhenius behavior at low temperatures. This dynamic crossover is independent of whether water at very low temperature is characterized by a "liquid-liquid critical point" or by the "singularity-free" scenario. We relate tau to fluctuations of hydrogen bond network and show that the crossover found for tau for both scenarios is a consequence of the sharp change in the average number of hydrogen bonds at the temperature of the specific heat maximum. We find that the effect of pressure on the dynamics is strikingly different in the two scenarios, offering means to distinguish between them.
通过对水的细胞模型进行蒙特卡罗模拟和平均场计算,我们发现取向关联时间τ存在动态转变,即从高温下的非阿仑尼乌斯行为转变为低温下的阿仑尼乌斯行为。这种动态转变与极低温下水是由“液 - 液临界点”还是“无奇点”情形来表征无关。我们将τ与氢键网络的涨落联系起来,并表明在这两种情形下τ的转变都是比热最大值温度下平均氢键数急剧变化的结果。我们发现,在这两种情形下压力对动力学的影响显著不同,这为区分它们提供了方法。