Projected Complex Absorbing Potential Multireference Configuration Interaction Approach for Shape and Feshbach Resonances.

Abstract

Anion resonances are formed as metastable intermediates in low-energy electron-induced reactions. Due to the finite lifetimes of resonances, applying standard Hermitian formalism for their characterization presents a vexing problem for computational chemists. Numerous modifications to conventional quantum chemical methods have enabled satisfactory characterization of resonances, but specific issues remain, especially in describing two-particle one-hole (2p-1h) resonances. An accurate description of these resonances and their coupling with single-particle resonances requires a multireference approach. We propose a projected complex absorbing potential (CAP) implementation within the multireference configuration interaction (MRCI) framework to characterize single-particle and 2p-1h resonances. As a first application, we use the projected-CAP-MRCI approach to characterize and benchmark the 2Πg shape resonance in N2-. We test its performance as a function of the size of the subspace and other parameters, and we compute the complex potential energy surface of the 2Πg shape resonance to show that a smooth curve is obtained. One key benefit of MRCI is that it can describe Feshbach resonances (most common examples of 2p-1h resonances) at the same footing as shape resonances. Therefore, it is uniquely positioned to describe mixing between the different channels. To test these additional capabilities, we compute Feshbach resonances in H2O- and anions of dicyanoethylene isomers. We find that CAP-MRCI can efficiently capture the mixing between the Feshbach and shape resonances in dicyanoethylene isomers, which has significant consequences for their lifetimes.