Ambiguities in solvation free energies from cluster-continuum quasichemical theory: lithium cation in protic and aprotic solvents.
KAUST DepartmentChemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Permanent link to this recordhttp://hdl.handle.net/10754/670266
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AbstractGibbs 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.
CitationItkis, D., Cavallo, L., Yashina, L. V., & Minenkov, Y. (2021). Ambiguities in solvation free energies from cluster-continuum quasichemical theory: lithium cation in protic and aprotic solvents. Physical Chemistry Chemical Physics. doi:10.1039/d1cp01454d
SponsorsWe 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.
PublisherRoyal Society of Chemistry (RSC)
Except where otherwise noted, this item's license is described as This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.
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