A Maxwell relation for dynamical timescales with application to the pressure and temperature dependence of water self-diffusion and shear viscosity
A Maxwell relation for dynamical timescales with application to the pressure and temperature dependence of water self-diffusion and shear viscosity
复制标题
动态时间尺度的麦克斯韦关系及其应用于水自扩散和剪切粘度的压力和温度依赖性
DOI：
10.1039/d3cp01386c
复制
发表时间：
2023
影响因子：
3.3
通讯作者：
Thompson, Ward H.
中科院分区：
文献类型：
--
作者：
Piskulich, Zeke A.;Borkowski, Ashley K.;Thompson, Ward H.
介绍并讨论了在恒压 p 和温度 T 下获得的反应速率常数（或其他动态时间尺度）的麦克斯韦关系。在波动理论的背景下检查这种关系可以深入了解时间尺度的 p 和 T 依赖性以及潜在的分子起源。这种麦克斯韦关系激发了对作为压力和温度函数的时间尺度的一般形式的建议。这是通过精确拟合模拟结果和液态水自扩散系数和剪切粘度的现有实验数据来说明的。这种方法的一个关键优点是每个拟合参数都具有物理意义。
A Maxwell relation for a reaction rate constant (or other dynamical timescale) obtained under constant pressure, p, and temperature, T, is introduced and discussed. Examination of this relationship in the context of fluctuation theory provides insight into the p and T dependence of the timescale and the underlying molecular origins. This Maxwell relation motivates a suggestion for the general form of the timescale as a function of pressure and temperature. This is illustrated by accurately fitting simulation results and existing experimental data on the self-diffusion coefficient and shear viscosity of liquid water. A key advantage of this approach is that each fitting parameter is physically meaningful.