Modeling anionic states is a frontier challenge for electronic structure methods. Commonly used semi-local and hybrid density functional approximations often underestimate electron affinities due to an incorrect long-range potential resulting from self-interaction errors and lack of long-range correlation effects. Here I will show that the effective potential from the generalized Kohn-Sham semicanonical projected random phase approximation (GKS-spRPA) method has the correct long-range behavior necessary for the description of anionic states. One-particle eigenvalues of the GKS-spRPA effective Hamiltonian provide excellent estimates of molecular electron attachment energies for valence and nonvalence anionic states. Using an improved O(N4) algorithm for GKS-spRPA, I will discuss interesting variations in the nature of anionic states in perhalobenzene molecules.

Molecular electron affinities using the generalized Kohn-Sham random phase approximation method

ACS Fall 2021

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