The effect of isodensity surface sampling on ESP derived charges and the effect of adding bondcenters on DMA derived charges.

Abstract

The effect of sampling the electrostatic potential around a molecule on the quality of electrostatic potential derived charges is investigated. In addition, the effect of the number of expansion sites in a Distributed Multipole Analysis (DMA) on the quality of charges fitted to the DMA derived electrostatic potential is investigated. Sampling on constant electron density surfaces gives a better fit between the quantum mechanical potential and the potential derived from the fitted charges, compared to sampling on a van der Waals surface composed of intersecting spheres. The fit between the electrostatic potential derived from point charges and the quantum mechanical potential becomes poorer with increasing quality of the employed basis set. The inclusion of bond-centers into the calculations improves the fit between the Quantum Mechanical (QM) electrostatic potential and the DMA derived potential. The number of expansion sites needed for an accurate approximation of the QM electrostatic potential increases with increasing quality of the used basis set.