Photoelectron spectroscopic studies of multiphoton processes in molecular chlorine involving the 2 1∏g Rydberg state

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Abstract
Kinetic energy resolved electron detection is used to study resonance enhanced multiphoton ionization and dissociation of molecular chlorine via the 2 1∏g Rydberg state. In the two‐photon energy region between 63 000 and 73 600 cm−1, a long vibrational progression up to v’=15 associated with this intermediate gerade Rydberg state is observed. The regularity and magnitude of the vibrational spacing indicate that the 2 1∏g state, converging to the ionic ground state, has virtually unperturbed Rydberg character. However, the molecular signals in the photoelectron spectra show strong deviations from Franck–Condon behavior. In addition, intense electron signals arising from one‐photon ionization of excited chlorine atoms are observed. An interpretation in terms of a competition between electronic autoionization and dissociation from core‐excited molecular Rydberg states situated above the lowest ionization energy is presented. Some of the excited atomic states observed are indicative for Rydberg–Rydberg interactions at large internuclear distances in the dissociation channel.