Department of Chemistry, Kansas State University, Manhattan, Kansas 66506, USA.
J Chem Phys. 2011 Jul 28;135(4):044506. doi: 10.1063/1.3615718.
An extension of the traditional Kirkwood-Buff (KB) theory of solutions is outlined which provides additional fluctuating quantities that can be used to characterize and probe the behavior of solution mixtures. Particle-energy and energy-energy fluctuations for local regions of any multicomponent solution are expressed in terms of experimentally obtainable quantities, thereby supplementing the usual particle-particle fluctuations provided by the established KB inversion approach. The expressions are then used to analyze experimental data for pure water over a range of temperatures and pressures, a variety of pure liquids, and three binary solution mixtures - methanol and water, benzene and methanol, and aqueous sodium chloride. In addition to providing information on local properties of solutions it is argued that the particle-energy and energy-energy fluctuations can also be used to test and refine solute and solvent force fields for use in computer simulation studies.
本文概述了一种扩展的传统 Kirkwood-Buff（KB）溶液理论，该理论提供了额外的涨落量，可以用于描述和探测溶液混合物的行为。通过实验可获得的量来表达局部区域的粒子-能量和能量-能量涨落，从而补充了传统 KB 反演方法提供的常用粒子-粒子涨落。然后，使用这些表达式分析了在一系列温度和压力下的纯水、多种纯液体以及三种二元溶液混合物（甲醇和水、苯和甲醇以及氯化钠水溶液）的实验数据。除了提供有关溶液局部性质的信息外，还认为粒子-能量和能量-能量涨落也可用于测试和完善用于计算机模拟研究的溶质和溶剂力场。
