Chaotic autoionization of molecular Rydberg states

We investigate the energy exchange between a Rydberg electron and the molecular core in the regime where the Born-Oppenheimer approximation is violated. The theory developed allows the possibility for a strong energy exchange even for high orbital momentum of the electron when quantum defects are small. We establish the existence of a classical chaos border and of a quantum delocalization border above which diffusive autoionization of the electron takes place. The relevance of theory for autoionization of doubly excited Rydberg atoms is also discussed.

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