A three-dimensional reduction of the Ornstein-Zernicke equation for molecular liquids
A three-dimensional reduction of the Ornstein-Zernicke equation for molecular liquids
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DOI：
10.1063/1.474300
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发表时间：
1997-10-22
影响因子：
4.4
通讯作者：
Friesner, RA
中科院分区：
文献类型：
--
作者：
Cortis, CM;Rossky, PJ;Friesner, RA
推导了溶质分子-溶剂位关联函数的三维积分方程。该方程是通过平均的Ornstein-Zernicke方程的分子液体的溶剂分子的取向一致的溶剂的一个网站保持在一个固定的距离从溶质为基础的起源。该方法是类似的，在减少导致参考相互作用网站模型（RISM）方程，但保留了完整的三维信息的参考溶质分子的结构。所提出的方程可以解决使用三维HNC样的封闭，其中三种不同的形式进行了讨论。还提出了一个配方，允许通过重整化方程的长程相互作用的介绍。各种分子液体的应用表明，所提出的理论提供了对相关函数，在更好的协议与分子动力学模拟比那些使用扩展RISM制定。此外，定性误差的相关函数，经常看到的结果从RISM计算完全消除通过几何平均的迈耶函数在3D HNC封闭。展望了一个新的平均场理论的溶剂化的发展进行了讨论。(C)1997年美国物理学会。
The derivation of a three-dimensional integral equation for solute molecule-solvent site correlation functions is presented. The equation is obtained by averaging the Ornstein-Zernicke equation for molecular liquids over orientations of the solvent molecule consistent with one site of the solvent remaining at a fixed distance from a solute-based origin. The approach is similar to that adopted in the reduction leading to the reference interaction site model (RISM) equations but retains full three-dimensional information regarding the structure of the reference solute molecule. The proposed equation can be solved using three-dimensional HNC-like closures, of which three different forms are discussed. A formulation which allows the introduction of long range interactions through a renormalization of the equation is also presented. Applications to various molecular liquids indicate that the proposed theory provides pair correlation functions that are in better agreement with molecular dynamics simulations than those obtained using the extended RISM formulation. Furthermore, qualitative errors in the correlation functions, frequently seen in results from RISM calculations are completely eliminated through geometrical averaging of the Mayer function in the 3D HNC closure. Prospects for the development of a novel mean field theory of solvation are also discussed. (C) 1997 American Institute of Physics.