Systematics of Rydberg structure in the spectra of the rare gas dimers between the atomic 2Po3/2 and 2Po1/2 fine-structure thresholds

Publisher Website
Google Scholar
Abstract
The relative photoionization cross sections for the rare gas dimers Ar2, Kr2, and Xe2 were measured in the energy region between the respective atomic 2P3/2o and 2P1/2o fine‐structure thresholds at wavelength resolutions of 0.15 Å for Ar2, 0.28 Å for Kr2, and 0.45 Å for Xe2. Discrete autoionization structure was observed for all three systems and has been partially analyzed in terms of Rydberg series converging to the C 2Π1/2u state of the molecular ions. Vertical binding energies for the individual Rydberg states were estimated based on the assumption that the Rydberg states dissociate to a rare gas atom in an ns′[1/2]1o or nd′[3/2]1o excited state plus a rare gas atom in the 1S0 ground state. The binding energies thus obtained are in excellent agreement with the corresponding values for the C 2Π1/2u ionic states obtained from previously reported photoelectron spectra. Some of the molecular structure exhibits Beutler–Fano profiles similar to those observed in the nd′[3/2]1o atomic series. This is in contrast to the energy region near the first ionization threshold, where it is extremely difficult to find a simple correlation between the atomic and molecular Rydberg structure.