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Hydration of Kr(aq) in Dilute and Concentrated Solutions
Mangesh I Chaudhari1,2,3,4, Dubravko Sabo1,2,3,4, Lawrence R Pratt1,2,3,4
1Center for Biological and Material Sciences, Sandia National Laboratories, Albuquerque, New Mexico 87123, United States.
Abstract:
Molecular dynamics simulations of water with both multi-Kr and single Kr atomic solutes are carried out to implement quasi-chemical theory evaluation of the hydration free energy of Kr(aq). This approach obtains free energy differences reflecting Kr-Kr interactions at higher concentrations. Those differences are negative changes in hydration free energies with increasing concentrations at constant pressure. The changes are due to a slight reduction of packing contributions in the higher concentration case. The observed Kr-Kr distributions, analyzed with the extrapolation procedure of Krüger et al., yield a modestly attractive osmotic second virial coefficient, B2 ≈ -60 cm(3)/mol. The thermodynamic analysis interconnecting these two approaches shows that they are closely consistent with each other, providing support for both approaches.
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