American Chemical Society
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Projected Complex Absorbing Potential Multireference Configuration Interaction Approach for Shape and Feshbach Resonances

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journal contribution
posted on 2022-05-27, 18:07 authored by Mushir Thodika, Spiridoula Matsika
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.