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Title: Experimental triplet and quadruplet fluctuation densities and spatial distribution function integrals for pure liquids

Fluctuation solution theory has provided an alternative view of many liquid mixture properties in terms of particle number fluctuations. The particle number fluctuations can also be related to integrals of the corresponding two body distribution functions between molecular pairs in order to provide a more physical picture of solution behavior and molecule affinities. Here, we extend this type of approach to provide expressions for higher order triplet and quadruplet fluctuations, and thereby integrals over the corresponding distribution functions, all of which can be obtained from available experimental thermodynamic data. The fluctuations and integrals are then determined using the International Association for the Properties of Water and Steam Formulation 1995 (IAPWS-95) equation of state for the liquid phase of pure water. The results indicate small, but significant, deviations from a Gaussian distribution for the molecules in this system. The pressure and temperature dependence of the fluctuations and integrals, as well as the limiting behavior as one approaches both the triple point and the critical point, are also examined.
Authors:
; ;  [1]
  1. Department of Chemistry, Kansas State University, 213 CBC Building, Manhattan, Kansas 66506 (United States)
Publication Date:
OSTI Identifier:
22416052
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 4; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AFFINITY; DENSITY; DISTRIBUTION FUNCTIONS; EQUATIONS OF STATE; FLUCTUATIONS; GAUSS FUNCTION; LIQUIDS; MATHEMATICAL SOLUTIONS; MOLECULES; PARTICLES; SPATIAL DISTRIBUTION; TEMPERATURE DEPENDENCE; TRIPLE POINT; TRIPLETS; TWO-BODY PROBLEM; WATER