Ambiguities in solvation free energies from cluster-continuum quasichemical theory: lithium cation in protic and aprotic solvents.

Daniil Itkis, Luigi Cavallo, Lada V Yashina, Yury Minenkov

Research output: Contribution to journalArticlepeer-review

10 Scopus citations


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. With n independent solvent molecules S initial state forming the "monomer" thermodynamic cycle, Li+ solvation free energies are found to be on average 14 kcal mol-1 more 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 Sn from the SMD and CPCM continuum solvation models, which is in line with the earlier study of Bryantsev et 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.
Original languageEnglish (US)
JournalPhysical chemistry chemical physics : PCCP
StatePublished - Jul 22 2021

Bibliographical note

KAUST Repository Item: Exported on 2021-07-26
Acknowledgements: We gratefully acknowledge Dr Dmitry I. Sharapa, Institute of Catalysis Research and Technology, Karlsruhe Institute of Technology (KIT), Germany; Dr Denis S. Tikhonov, Deutsches Elektronen-Synchrotron (DESY), Hamburg, Germany; Dr Alexander Genaev, N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Novosibirsk, Russia, for helpful discussionsWe also acknowledge the anonymous reviewers of this work for their useful comments and suggestions. This work was financially supported by the Russian Science Foundation (project 19-43-04112). L. C. gratefully acknowledges the financial support from King Abdullah University of Science and Technology (KAUST). 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.

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


Dive into the research topics of 'Ambiguities in solvation free energies from cluster-continuum quasichemical theory: lithium cation in protic and aprotic solvents.'. Together they form a unique fingerprint.

Cite this