Hartree-fock transition theory and multi-electron transitions in atoms and molecules

Abstract

Multi-electron transitions can be induced via electron correlation. However, in many cases, such transitions can also be understood in terms of orbital relaxation and their probability can be estimated from the N-electron Hartree-Fock theory of transitions. Thus, even when complex algorithms. like the RPA, fail, heuristic as well as semi-quantitative predictions on the dynamics of transitions can often be made based on true Hartee-Fock functions only. The present point of view is supported by numerical results for a variety of cases, including the first prediction for He − 1s2s2p 4P 0 double photoionization into the 4P channel.