Investigation of negative-ion resonances using a subspace-projected multiconfigurational electron propagator perturbed with a complex absorbing potential.

Abstract

The transient negative-ion resonances found in scattering experiments are important intermediates in many chemical processes. These metastable states correspond to the continuum part of the Hamiltonian of the projectile-target composite system. Usual bound-state electronic structure methods are not applicable for these. In this work, we develop a subspace-projection method in connection with an electron propagator (EP) defined in terms of a complete-active-space self-consistent-field initial state. The target Hamiltonian (Ĥ) is perturbed by a complex absorbing potential (CAP) for the analytical continuation of the spectrum of Ĥ to complex eigenvalues associated with the continuum states. The resonance is identified as a pole of the EP, which is stable with respect to variations in the strength of the CAP. The projection into a small subspace reduces the size of the complex matrices to be diagonalized, minimizes the computational cost, and affords some insight into the orbitals that are likely to play some role in the capture of the projectile. Two molecular (Πg2N2 - and 2Π CO-) and an atomic shaperesonance (2P Be-) are investigated using this method. The position and width of the resonances are in good agreement with the previously reported values.