TY - JOUR
T1 - Cluster-Continuum Model as a Sanity Check of Sodium Ions’ Gibbs Free Energies of Transfer
AU - Otlyotov, Arseniy A.
AU - Cavallo, Luigi
AU - Minenkov, Yury
N1 - KAUST 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.
PY - 2022/11/7
Y1 - 2022/11/7
N2 - 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.
AB - 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.
UR - http://hdl.handle.net/10754/685648
UR - https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c02065
U2 - 10.1021/acs.inorgchem.2c02065
DO - 10.1021/acs.inorgchem.2c02065
M3 - Article
C2 - 36343158
SN - 0020-1669
JO - Inorganic Chemistry
JF - Inorganic Chemistry
ER -