The first absolute photoion-pair cross sections have been derived from measurements of the absolute photoabsorption cross section and the photoion-pair quantum efficiency. The results for CH3Cl, CH3Br and CF2Cl2 show that direct transitions into ion-pair states play a significant role. In each molecule, the structure in the photoion-pair spectrum is different to that in the photoabsorption spectrum and often does not resemble the strong bands, due to Rydberg transitions, prominent in the latter spectra. At photon energies associated with excitations into Rydberg states, and consequently with peaks in absorption, the photoion-pair quantum efficiency usually exhibits a local minimum. This indicates that the Rydberg state decays preferentially by predissociation into a state yielding neutral fragments rather than by predissociation into a state evolving into ion pairs. © 2006 IOP Publishing Ltd.
|Number of pages||12|
|Journal||Journal of Physics B: Atomic, Molecular and Optical Physics|
|Publication status||Published - 14 Sep 2006|