Quantitative Solvation Energies from Gas-Phase Calculations: First-Principles Charge Transfer and Perturbation Approaches

Ramón Alain Miranda-Quintana; Lexin Chen; Vincent S J Craig; Jens Smiatek

doi:10.1021/acs.jpcb.2c08907

Quantitative Solvation Energies from Gas-Phase Calculations: First-Principles Charge Transfer and Perturbation Approaches

J Phys Chem B. 2023 Mar 23;127(11):2546-2551. doi: 10.1021/acs.jpcb.2c08907. Epub 2023 Mar 14.

Authors

Ramón Alain Miranda-Quintana¹, Lexin Chen², Vincent S J Craig³, Jens Smiatek⁴

Affiliations

¹ Department of Chemistry and Quantum Theory Project, University of Florida, Gainesville, Florida 32603, United States.
² Department of Chemistry, University of Florida, Gainesville, Florida 32603, United States.
³ Department of Applied Mathematics, Research School of Physics and Engineering, The Australian National University, Canberra, Australian Capital Territory 2601, Australia.
⁴ Institute for Computational Physics, University of Stuttgart, D-70569 Stuttgart, Germany.

PMID: 36917810
DOI: 10.1021/acs.jpcb.2c08907

Abstract

We present a first-principles approach for the calculation of solvation energies and enthalpies with respect to different ion pair combinations in various solvents. The method relies on the conceptual density functional theory (DFT) of solvation, from which detailed expressions for the solvation energies can be derived. In addition to fast and straightforward gas phase calculations, we also study the influence of modified chemical reactivity descriptors in terms of electronic perturbations. The corresponding phenomenological changes in molecular energy levels can be interpreted as the influence of continuum solvents. Our approach shows that the introduction of these modified expressions is essential for a quantitative agreement between the calculated and the experimental results.