The effect of electron correlation on the electron density distributions of molecules: Comparison of perturbation and configuration interaction methods

Abstract

Two methods for including the effects of electron correlation on the electron density distributions of molecules are compared. Second-order Mo/ller–Plesset perturbation theory (MP2) is shown to give electron density distributions in good qualitative agreement with much more time-consuming configuration interaction calculations. The latter include all single and double substitutions from the Hartree–Fock reference configuration. The two methods are compared by means of difference density maps calculated with large basis sets for a few representative molecules. From an analysis of the relative importance of single and double substitutions, it is shown that double substitutions are dominant near nuclei, but in other regions of space the single substitutions are more important. The MP2 method is shown to provide a practical method for calculating the correlation corrections to the electron density distributions of molecules of intermediate size.