TY - JOUR
T1 - Ambiguities in solvation free energies from cluster-continuum quasichemical theory: lithium cation in protic and aprotic solvents.
AU - Itkis, Daniil
AU - Cavallo, Luigi
AU - Yashina, Lada V
AU - Minenkov, Yury
N1 - 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.
PY - 2021/7/22
Y1 - 2021/7/22
N2 - 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.
AB - 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.
UR - http://hdl.handle.net/10754/670266
UR - http://xlink.rsc.org/?DOI=D1CP01454D
U2 - 10.1039/d1cp01454d
DO - 10.1039/d1cp01454d
M3 - Article
C2 - 34291782
SN - 1463-9076
JO - Physical chemistry chemical physics : PCCP
JF - Physical chemistry chemical physics : PCCP
ER -