Analytic evaluation of non-adiabatic couplings within the complex absorbing potential equation-of-motion coupled-cluster method

K. Chatterjee, Z. Koczor-Benda, X. Feng, A.I. Krylov, and T.-C. Jagau
J. Chem. Theo. Comp.  19, 5281 – 5834 (2023)

We present the theory for the evaluation of non-adiabatic couplings (NACs) involving resonance states within the complex absorbing potential equation-of-motion coupled-cluster (CAP-EOM-CC) framework implemented within the singles and doubles approximation. Resonance states are embedded in the continuum and undergo rapid decay through autodetachment. In addition, nuclear motions can facilitate transitions between different resonances and between resonances and bound states. These non-adiabatic transitions affect the chemical fate of resonances and have distinct spectroscopic signatures. The NAC vector is a central quantity needed to model such effects. In the CAP-EOM-CC framework, resonance states are treated on the same footing as bound states. Using the example of fumaronitrile, which supports a bound radical anion and several anionic resonances, we analyze the non-adiabatic coupling between bound states and pseudocontinuum states, between bound states and resonances and between two resonances. We find that the NAC between a bound state and a resonance is nearly independent of the CAP strength and thus straightforward to evaluate whereas the NAC between two resonance states or between a bound state and a pseudocontinuum state is more difficult to evaluate.

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