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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.
Molecular dynamics simulations reveal hydration free energy of krypton(aq) using quasi-chemical theory. Increasing krypton concentrations show negative hydration free energy changes due to packing effects, yielding an attractive osmotic second virial coefficient.
Area of Science:
- Physical Chemistry
- Computational Chemistry
- Chemical Physics
Background:
- Understanding the hydration of atomic solutes like krypton (Kr) is crucial in physical chemistry.
- Quasi-chemical theory provides a framework for evaluating hydration free energies.
Purpose of the Study:
- To evaluate the hydration free energy of aqueous krypton (Kr(aq)) using molecular dynamics simulations and quasi-chemical theory.
- To investigate the effects of Kr-Kr interactions at higher concentrations on hydration free energy.
Main Methods:
- Molecular dynamics (MD) simulations were performed for water with single and multiple krypton atomic solutes.
- Quasi-chemical theory was implemented to calculate hydration free energies.
- Kr-Kr radial distribution functions were analyzed using the Krüger et al. extrapolation procedure.
Main Results:
- Hydration free energies of Kr(aq) were calculated.
- Increasing krypton concentrations led to negative changes in hydration free energies at constant pressure.
- These changes were attributed to a reduction in packing contributions.
- A modestly attractive osmotic second virial coefficient (B2 ≈ -60 cm³/mol) was determined.
Conclusions:
- The quasi-chemical theory approach, combined with MD simulations, accurately determines hydration free energies and Kr-Kr interactions.
- The study demonstrates consistency between hydration free energy changes and the osmotic second virial coefficient.
- Findings support the validity of both the quasi-chemical theory and the extrapolation method for analyzing solute interactions.
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