An Electron Propagator Approach Based on a Multiconfigurational Reference State for the Investigation of Negative-Ion Resonances Using a Complex Absorbing Potential Method.

Abstract

Negative-ion resonances are important metastable states that result from the collision between an electron and a neutral target. The course of many chemical processes in nature is often dictated by how an intermediate resonance state falls apart. This article reports on the development of an electron propagator (EP) based on a Hamiltonian Ĥ perturbed by a complex absorbing potential (CAP) and a multiconfigurational self-consistent field (MCSCF) initial state to study these resonances. Perturbation of Ĥ by a CAP makes the resonances amenable to a bound-state method like MCSCF. Resonances stand out among the non-resonant states as persistent complex eigenvalues of the perturbed Ĥ when the strength (η) of the CAP is varied. The MCSCF method gives a reliable and accurate description of the target states, especially when the non-dynamical correlations are dominant. The resonance energies are obtained from the poles of the EP. We propose three variants of our EP depending on how the effect of the CAP is introduced. We find that the computationally most efficient variant is the one in which the reference state of the EP is an unperturbed MCSCF wavefunction and a non-zero CAP is defined only on the virtual orbital subspace of the reference state. The onset of the CAP is carefully optimized in order to minimize the artifacts due to reflections from the CAP. An extrapolation method (based on a Padé approximant) and a de-perturbation method are adopted in order to account for the limitations of finite basis sets used and determine the resonance energy in the limit of η → 0. 2P Be-, 2Πg N2-, and 2Π CO- shape resonances are investigated. The position and width of these resonances computed in this study agree well with those reported earlier in the literature.