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Ambiguities in solvation free energies from cluster-continuum quasichemical theory: lithium cation in protic and aprotic solventsстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 1 сентября 2021 г.
- Авторы: Itkis Daniil, Cavallo Luigi, Yashina Lada V., Minenkov Yury
- Журнал: Physical Chemistry Chemical Physics
- Том: 23
- Номер: 30
- Год издания: 2021
- Издательство: Royal Society of Chemistry
- Местоположение издательства: United Kingdom
- Первая страница: 16077
- Последняя страница: 16088
- DOI: 10.1039/d1cp01454d
- Аннотация: Gibbs free energies for Li+solvation in water, methanol, acetonitrile, DMSO, dimethylacetamide, dimethoxyethane, dimethylformamide, gamma-butyrolactone, pyridine, and sulfolane have been calculated using the cluster-continuum quasichemical theory. Withnindependent solvent molecules S initial state forming the “monomer” thermodynamic cycle, Li+solvation free energies are found to be on average 14 kcal mol−1more positive compared to those from the “cluster” thermodynamic cycle where the initial state is the cluster Sn. We ascribe the inconsistency between the “monomer” and “cluster” cycles mainly to the incorrectly predicted solvation free energies of solvent clusters Snfrom the SMD and CPCM continuum solvation models, which is in line with the earlier study of Bryantsevet al.,J. Phys. Chem. B, 2008,112, 9709-9719. When experimental-based solvation free energies of individual solvent molecules and solvent clusters are employed, the “monomer” and “cluster” cycles result in identical numbers. The best overall agreement with experimental-based “bulk” scale lithium cation solvation free energies was obtained for the “monomer” scale, and we recommend this set of values. We expect that further progress in the field is possible if (i) consensus on the accuracy of experimental reference values is achieved; (ii) the most recent continuum solvation models are properly parameterized for all solute-solvent combinations and become widely accessible for testing.
- Добавил в систему: Яшина Лада Валерьевна