FRAGMENTATION OF VALENCE ELECTRONIC STATES OF CF4+ AND SF6+ STUDIED BY THRESHOLD PHOTOELECTRON PHOTOION COINCIDENCE SPECTROSCOPY

Threshold photoelectron-photoion coincidence (TPEPICO) spectroscopy ha s been used to measure, state selectively, the decay pathways of all t he valence states of CF4+ and SF6+ in the range 15-28 eV. Radiation in the vacuum UV from a synchrotron radiation source ionises the parent molecule, and the electrons and ions are detected by threshold electro n analysis and time-of-flight mass spectroscopy, respectively. TPEPICO spectra are recorded continuously as a function of photon energy, all owing both threshold photoelectron spectra and yields of all the fragm ent ions to be obtained. Kinetic energy releases are measured at fixed photon energies with good time resolution. The results for the X 2T1, A 2T2 and B 2E states of CF4+ (all below the energy of He I radiation ) confirm earlier measurements; results for the C 2T2 and D 2A1 states at 21.7 and 25.1 eV, respectively, are new. They confirm previous mea surements that radiative decay from both states is an important proces s, and we have measured their state-selected fluorescence quantum yiel ds. For SF6+, fluorescence does not occur from any of the excited vale nce states, and we have measured the fragmentation channels and branch ing ratios for all of the valence states.