title: Lyman-α photodesorption from CO2(ice) at 75 K: role of CO2 vibrational relaxation on desorption rate.
abstract: The photodesorption of CO2 from CO2(ice) at 75 K when irradiated by Lyman-α light is strongly mediated by vibrational relaxation of highly vibrationally excited molecules produced from the electronically excited CO2 state. A vibrationally hot molecule can either relax (major process) in the ice or desorb (minor process). We find that isotopically pure CO2 ices photodesorb least efficiently due to efficient vibrational tuning between molecules in the ice. Isotopically impure CO2 ices are more poorly vibrationally relaxed and hence photodesorb more efficiently. Mixed CO2-Xe ices are still more efficiently photodesorbed due to the dilution of CO2, which further reduces the rate of vibrational relaxation. Resonant interactions as well as phonon-assisted interactions contribute to vibrational relaxation efficiency in ices, and inversely to photodesorption efficiency. The vibrational lifetime of hot CO2 in its ice at 75 K is of order of 10(-15) s. These results indicate that under astronomical conditions, the rate of photodesorption will depend inversely on the rate of vibrational quenching in the ice, which is dependent on the abundance and distance of like oscillators from each other in the ice. In rather isotopically pure ices, the minority isotopic species will photodesorb more rapidly.
authors.affiliation: Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, USA.
authors.forename: Chunqing
authors.initials: C
authors.lastname: Yuan
authors.forename: John T
authors.initials: JT
authors.lastname: Yates