An active mode in both the collision-free and collision-induced vibrational dynamics of S1 p-difluorobenzene

D. L. Catlett, K. W. Holtzclaw, D. Krajnovich, D. B. Moss, C. S. Parmenter, W. D. Lawrance, A. E.W. Knight

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

We present evidence that the vibrational mode v′30 = 119.7 cm-1, an out-of-plane fluorine bend, is specially active in collision-induced level-to-level vibrational energy transfer within S1 p-difluorobenzene (pDFB). We summarize other evidence that shows v′30 to be also an accelerating mode for collision-free intramolecular vibrational energy transfer in S1 pDFB. These are the first findings of a common accelerating mode for both collision-free and collision-induced vibrational energy redistribution. The common role can be understood with the proposition that level mixing in the isolated molecule plays a dominant role in both processes. We have examined possible mechanisms for the enhanced coupling of v′30: anharmonic mixing, Coriolis vibration-rotation mixing, and centrifugal vibration-rotation mixing. No single mechanism is identified as the source of the special activity of v′30.

Original languageEnglish
Pages (from-to)1577-1581
Number of pages5
JournalJournal of Physical Chemistry
Volume89
Issue number9
DOIs
Publication statusPublished - 1 Apr 1985
Externally publishedYes

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    Catlett, D. L., Holtzclaw, K. W., Krajnovich, D., Moss, D. B., Parmenter, C. S., Lawrance, W. D., & Knight, A. E. W. (1985). An active mode in both the collision-free and collision-induced vibrational dynamics of S1 p-difluorobenzene. Journal of Physical Chemistry, 89(9), 1577-1581. https://doi.org/10.1021/j100255a008