Dynamic aspects of electronic predissociation

We consider electronic excitation induced with a continuous wave laser to an excited bound state which can predissociate due to a radiationless transition to a dissociative state. The conditions for a separation of the process into the preparation of a vibrational eigenstate which subsequently dissociates due to a radiationless transition are established. We point out that the probability of the radiationless transition can be calculated from a time-dependent nuclear autocorrelation function, an expression which nicely reflects the pictorial aspect of the Franck-Condon principle. (C) 1996 American Institute of Physics.