PHOTOELECTRON-SPECTROSCOPY OF AUTOIONIZATION AND DISSOCIATION IN MOLECULAR CHLORINE USING RESONANCE ENHANCED MULTIPHOTON IONIZATION

Kinetic energy resolved electron detection is used to study resonance enhanced multiphoton ionization and dissociation via the 21Π g, state of molecular chlorine. In scanning the laser wavelength a long, regular vibrational progression up to v'= 15 is observed which demonstates the virtually unperturbed Rydberg character of 2 1Πg. The photoelectron spectra show molecular features with strong deviations from the expected Δv = 0 propensity, and atomic signals arising from electronically excited chlorine atoms. These observations indicate the importance of transitions to excited 3 1,3Πu states which decay via electronic autoionization and dissociation. © 1990.