Molecular Electron Affinities Using the Generalized Kohn-Sham Semicanonical Projected Random Phase Approximation.

Abstract

The suitability of one-particle energies from the generalized Kohn-Sham semicanonical projected random phase approximation (GKS-spRPA) method for electron affinities of molecules is investigated. It is shown that the GKS-spPRA effective potential includes exact exchange and polarizability-dependent correlation terms that are necessary for the correct description of anionic systems. An implementation that enables fast computation of electron affinities is presented. For model systems, I show that the GKS-spRPA approach is applicable for valence and nonvalence type anions with a maximum error of 0.13 eV for valence anionic states and 0.03 eV for nonvalence anionic states compared to equation of motion coupled cluster methods. For a series of perhalobenzene molecules, C6X6 (X= F, Cl, Br, and I), GKS-spRPA predicts that the ground-state character changes from a nonvalence-σ* type in C6F6- to valence-π* in C6Cl6- and valence-σ* in C6Br6- and C6I6-. Experimental implications of these findings are discussed.