PHOTODETACHMENT IN THE GASEOUS, LIQUID, AND SOLID STATES OF MATTER

We have made absolute cross section measurements of laser photodetachment of C6F6- ions embedded in gaseous tetramethylsilane (TMS) and compared the results at low gas densities with measurements in nonpolar liquids and solids. The measurements indicate that the photodetachment cross section of C6F6- in gaseous TMS is about three times larger than in liquid TMS. This is rationalized by considering the effect of the medium on both the photoabsorption and the autodetachment processes. The photodetachment cross section in both the gas and the liquid exhibits (at least) two maxima due to autodetaching negative ion states. It is argued that these are due to sigma*-->sigma* transitions in C6F6-. The relative positions of these ''superexcited'' anionic states did not change appreciably in going from the gas to the liquid and the solid, indicating similar influences of the medium on them. As expected, the photodetachment threshold in the condensed phase is shifted to higher energies compared to the gaseous phase. This shift is consistent with recent photoelectron studies of photodetachment of C6F6- clusters. The present study clearly shows that the photodetachment from negative ions embedded in all states of matter proceeds directly or indirectly via negative ion autodetaching states, and that for nonpolar media, the effect of the medium can be accounted for by considering the macroscopic properties of the medium described by its dielectric constant epsilon and refractive index n.