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 qu
antum defects are small. We establish the existence of a classical cha
os border and of a quantum delocalization border above which diffusive
autoionization of the electron takes place. The relevance of theory f
or autoionization of doubly excited Rydberg atoms is also discussed.