Feshbach projection XMCQDPT2 model for metastable electronic states

Abstract

Autoionizing electronic states are common intermediates in processes initiated by electron impact or high-energy radiation. These states belong to the continuous spectrum of the Hamiltonian, and as such cannot be treated with methods developed for bound electronic states. Here we propose a new model for describing metastable electronic states, which combines discretized Feshbach projection formalism and multireference perturbation theory and exploits absorbing potential to generate the basis of the coupled valence state and continuum. The results of benchmark calculations for a series of shape resonances in polyatomic molecules are in good agreement with experimental and theoretical reference values.