Cost-effective methods for accurate calculation of ion-solvent binding energies

Abstract

This paper presents a benchmarking study of DFT functionals and basis sets for the calculation of molecular geometries and binding energies of ion-solvent clusters. The systems examined include various monoatomic and polyatomic ions in water, methanol, and DMSO clusters. The use of high-quality triple-ζ basis sets is recommended for calculation of geometries though less-costly double-ζ basis set can often give good results due to systematic error cancellation. ωB97X-V and ωB97M-V are the two best-performing methods for single point energy calculation with mean errors well below the threshold of chemical accuracy (∼5 kJ mol⁻¹) relative to DLPNO-CCSD(T)/CBS and revDSD-PBEP86-D4/def2-TZVPPD benchmarks.