Journal of Chemical Physics, Vol.101, No.6, 4628-4634, 1994
The Effect of Methane on Photocurrents Generated by Exciting Xenon Below Its First Ionization-Potential
Photocurrent excitation spectra of xenon and of the xenon-methane absorber-perturber system were studied in cells equipped with LiF windows cooled to approximate to-30 degrees C. The cooling was needed to shift the LiF cutoff so as to enable measurements at photon energies up to the first ionization potential of Xe (12.13 eV). The spectra observed in methane-xenon mixtures were essentially similar to those in neat xenon, demonstrating that the Hornbeck-Molnar process (excitation of a xenon atom-excimer formation-ionization of an excimer) is feasible even in the presence of the molecular perturber CH4 at pressures up to approximate to 10(5) Pa. The primary effect of CH4 is to decrease the photocurrent, since photons in the energy range in question are absorbed by the methane molecules as well, without photoionizing them. The dependence of the current on methane concentration showed that the above mechanism is not the only one by which methane quenches the current. Moreover, the degree of quenching of the current by methane is dependent on the photon energy. The analysis of this dependence led to the assumption that an excited xenon atom and a methane molecule may form an excimer. Previous results on the Ar:Xe and Kr:Xe systems support this assumption. Peak inversions observed at high pressures in neat xenon, but absent in the CK4:Xe system, are discussed on the basis of prevailing models.
Keywords:VACUUM ULTRAVIOLET;PHOTO-IONIZATION;RYDBERG SERIES;PHOTOCONDUCTIVITY;PHOTOIONIZATION;ABSORPTION;IMPURITY;STATES;AUTOIONIZATION;SPECTROSCOPY