Autoionization of nonpenetrating Rydberg states of NO and H2

New experiments are reported on vibrational autoionization in the nf Rydberg states of NO and H2. Since these states are nonpenetrating, the core interactions that normally lead to autoionization are very weak. Autoionization of these nonpenetrating Rydberg states can be caused by the long-range interaction of the Rydberg electron with the multiple moments and polarizability of the molecular ion core. Results for the 4f, v = 3 state of NO suggest that the decay, with deltav= -3, is influenced significantly by perturbations with other Rydberg states. Preliminary work on the nf, v = 1 states of H2 is in approximate quantitative agreement with the long-range model, but still reveals at least one anomaly due to perturbations. The first portion of this paper describes the long-range autoionization process, which probably dominates the decay of most high l Rydberg states. The second and third portions describe the experiments on NO and H2. 12 references, 6 figures