CAP/EA-ADC method for metastable anions: Computational aspects and application to pi* resonances of norbornadiene and 1,4-cyclohexadiene

摘要

The second- and third-order algebraic-diagrammatic construction schemes for the electron propagator for studies of electron attachment processes [EA-ADC(2) and EA-ADC(3)] have been extended to include the complex absorbing potential (CAP) method for the treatment of electronic resonances. Theoretical and conceptual aspects of the new CAP/EA-ADC methodology are studied in detail at the example of the well-known (2)pi(g) resonance of the nitrogen anion N-2(-). The methodology is further applied to pi* shape resonances, for which ethylene is considered as a prototype. Furthermore, the first many-body treatment of the pi(+)* and pi(-)* resonances of norbornadiene and 1,4-cyclohexadiene is provided, which have served as model systems for the concept of through-space and through-bond interactions for a long time.