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NeCl2 and ArCl2: transition from direct vibrational predissociation to intramolecular vibrational relaxation and electronic nonadiabatic effects†

AuthorsR. Bieler, Craig; Janda, Kenneth C.; Hernández Lamoneda, Ramón; Roncero, Octavio CSIC ORCID
Issue Date15-Sep-2010
PublisherAmerican Chemical Society
CitationJournal of Physical Chemistry A 114 (9): 3050–3059 (2010)
AbstractPump−probe results are reported for NeCl2 excited to the Cl2 B state, undergoing vibrational predissociation, and then probed via E ← B transitions. Intensities, lifetimes and product vibrational branching ratios are reported for 16 ≤ v′ ≤ 19 Cl2 stretching quanta. The intensity of the signal rapidly decreases above v′ = 17. Detailed wave packet calculations of the vibrational predissociation dynamics are performed to determine if the experimental results can be explained by the onset of IVR dynamics. The calculations and the experiment are in close accord for low vibrational levels. For higher levels, some, but not all, of the loss of experimental signal can be attributed to IVR. To test whether electronic relaxation dynamics are important for NeCl2 and ArCl2, excited state potential surfaces that incorporate spin orbit coupling effects are calculated. These surfaces are then used in a wave packet calculation that includes both vibrational predissociation and electronic predissociation dynamics. The results show that electronic predissociation is important for ArCl2 levels above v′ = 12. For NeCl2 the calculation suggests that the onset of electronic predissociation should occur for levels as low as v′ = 13 but may not contribute markedly to the observed loss of signal above v′ = 17. Suggestions are made for further studies of this puzzling problem.
Description10 pags. ; 7 figs. This article is part of the A: Benoit Soep Festschrift special issue.
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