Polarization-corrected molecular electrostatic potential for the cation binding problem

Abstract

The molecular electrostatic potential (MESP) and polarization-corrected MESP (PMESP) minima for some small molecules are calculated on the surface generated by rolling cations (Li⁺ and Na⁺) on their van der Waals surfaces. The cation binding energies of these molecules are obtained with HF/6-31G^∗∗ level ab initio calculations. A noteworthy outcome of the present study is that the plot of these binding energies and the corresponding PMESP surface minimum values turns out to be remarkably linear with a slope close to unity. The PMESP is thus found to work as a powerful tool for unearthing the patterns of cation binding sites and energetics for molecular systems.