Reliability of MEP and MEP-derived properties computed from DFT methods for molecules containing P, S and CL

Abstract.

We present a systematic study on the reliability of different theoretical methods to represent the molecular electrostatic potential (MEP), and MEP-derived properties of prototypical compounds containing phosphorus, sulfur and chlorine. Calculations at the Hartree-Fock and Møller-Plesset up to fourth-order level of theory, as well as local, non-local and hybrid density functional computations were performed for a representative set of neutral molecules. The study was carried out using different basis sets ranging from the medium-sized 6-31G(d ) to the large 6-31G(2d,2p) basis set, but in some test calculations more extended basis sets were also considered. The analysis of the results was performed discussing separately the effect of the basis set and of the level of theory used to determine the molecular wavefunction on the reliability of the MEP and MEP-derived properties.