title: Local fluctuations in solution mixtures.
abstract: 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.
authors.affiliation: Department of Chemistry, Kansas State University, Manhattan, Kansas 66506, USA.
authors.forename: Elizabeth A
authors.initials: EA
authors.lastname: Ploetz
authors.forename: Paul E
authors.initials: PE
authors.lastname: Smith
mesh_terms: D001554:Benzene / Q000737:chemistry*; D003198:Computer Simulation; D000432:Methanol / Q000737:chemistry*; D008956:Models, Chemical; D012965:Sodium Chloride / Q000737:chemistry*; D012996:Solutions / Q000737:chemistry; D013696:Temperature; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
chemical_list: D012996:Solutions; D014867:Water; D012965:Sodium Chloride; D001554:Benzene; D000432:Methanol