An approach to estimate the uncertainty of the calculated through the monomer cycle cluster-continuum model Gibbs free energy of transfer has been developed and suggested to be used as a quantitative measure of the reliability of the predictions. A set of experimental Na+ free energies of transfer from water to 18 solvents (ΔGtr(Na+, W → S)) has been assessed. For all solvents, we find Na+(S)n clusters to be thermodynamically unstable if n > 5. For 1,2-dichloroethane (1,2-DCIE), we have resolved considerable (ca. 10 kcal mol–1) discrepancies between available experimental ΔGtr(Na+, W → S). For 1,1-DCIE, we reject the only available experimental value and recommend our own estimate instead. We strongly propose experimental revisiting of ΔGtr(Na+, W → S) for ethylene glycol and hexamethylphosphoramide. The statistical analysis performed on a set of predicted and recommended experimental ΔGtr(Na+, W → S) values, in this work, results in the mean unsigned and signed deviations of 3.4 and −1.3 kcal mol–1, respectively. The squared Pearson correlation coefficient of 0.91 encourages the extension of the utilized theoretical approach to other available experimental data on ion solvation.
Bibliographical noteKAUST Repository Item: Exported on 2022-11-14
Acknowledgements: The work was financially supported by the Russian Science Foundation (project 22-23-20206). L.C. gratefully acknowledges the financial support from the King Abdullah University of Science and Technology (KAUST). Anna Minenkova is gratefully acknowledged for her assistance in the preparation of the TOC figure. The authors also acknowledge the anonymous reviewers of this work for their useful comments and suggestions. For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science and Technology (KAUST) in Thuwal, Saudi Arabia, and the Joint Supercomputer Center of RAS in Moscow, Russia.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry