Ab Initio Complex Transition Dipoles between Autoionizing Resonance States from Real Stabilization Graphs.

Abstract

Electronic transition dipoles are crucial for investigating light-matter interactions. Transition dipoles between metastable (autoionizing resonance) states become complex within non-Hermitian formalism, analogous to the resonance energies. Herein, we put forward a robust method for evaluating complex transition dipoles based on real ab initio stabilization calculations. The complex transition dipoles are obtained by analytical continuation via the Padé approximant and are identified as stationary solutions in the complex plane. The capability of the new approach is demonstrated for several transition dipoles of the doubly excited helium resonance states, for which exact values are available for comparison. Nevertheless, the method presented here has no inherent limitation and is suitable for polyatomic systems.