Collect. Czech. Chem. Commun. 2008, 73, 733-744

The Onset of Ion Solvation by ab initio Calculations: Comparison of Water and Methanol

Eva Pluhařová and Pavel Jungwirth*

Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, v.v.i. and Center for Biomolecules and Complex Molecular Systems, Flemingovo nám. 2, 166 10 Prague 6, Czech Republic


Optimal structures as well as vertical and adiabatic desolvation energies for sodium cation and fluoride and chloride anions in clusters with one to three water or methanol molecules are determined using converging ab initio methods (MP2/aug-cc-pvtz for geometries and CCSD(T) in the complete basis set limit for energetics). The results, which are in good agreement with previous calculations and experiments (if available), show that in small clusters the interactions of ions with methanol are stronger than those with water. Only upon adding more solvent molecules the situation starts to revert, approaching thus the bulk limit where water is a better solvent for alkali metal cations and halide anions than methanol.

Keywords: Clusters; Ion solvation; Ab initio calculations; Salts; NaF; sodium fluoride.

References: 28 live references.