van Zon Ramses, Schofield Jeremy
The Rockefeller University, 1230 York Avenue, New York, New York 10021-6399, USA.
J Phys Chem B. 2005 Nov 17;109(45):21425-36. doi: 10.1021/jp052234g.
The theoretical framework for higher-order correlation functions involving multiple times and multiple points in a classical, many-body system developed by Van Zon and Schofield [Phys. Rev. E 2002, 65, 011106] is extended here to include tagged particle densities. Such densities have found an intriguing application as proposed measures of dynamical heterogeneities in structural glasses. The theoretical formalism is based upon projection operator techniques which are used to isolate the slow time evolution of dynamical variables by expanding the slowly evolving component of arbitrary variables in an infinite basis composed of the products of slow variables of the system. The resulting formally exact mode-coupling expressions for multiple-point and multiple-time correlation functions are made tractable by applying the so-called N-ordering method. This theory is used to derive for moderate densities the leading mode coupling expressions for indicators of relaxation type and domain relaxation, which use dynamical filters that lead to multiple-time correlations of a tagged particle density. The mode coupling expressions for higher order correlation functions are also successfully tested against simulations of a hard sphere fluid at relatively low density.
范宗和斯科菲尔德[《物理评论E》2002年,65卷,011106期]所建立的关于经典多体系统中涉及多个时间点和多个空间点的高阶关联函数的理论框架,在此扩展到包含标记粒子密度的情况。这种密度作为结构玻璃中动力学非均匀性的一种提议度量,已发现其有趣的应用。该理论形式基于投影算符技术,通过在由系统慢变量的乘积组成的无限基中展开任意变量的慢演化分量,来分离动力学变量的慢时间演化。通过应用所谓的N排序方法,使所得的多点和多时间关联函数的形式上精确的模式耦合表达式变得易于处理。该理论用于在中等密度下推导弛豫类型和域弛豫指标的主导模式耦合表达式,这些表达式使用导致标记粒子密度多时间关联的动力学滤波器。高阶关联函数的模式耦合表达式也在相对低密度的硬球流体模拟中得到了成功验证。