Rovibrational energy transfer in the 4vCH manifold of acetylene viewed by IR-UV double resonance spectroscopy. 2. Perturbed states with J = 17 and 18

Mark A. Payne, Angela P. Milce, Michael J. Frost, Brian J. Orr

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Collision-induced state-to-state molecular energy transfer between rovibrational states in the 12 700 cm-1 4vCH manifold of the electronic ground state X~ of acetylene (C2H2) is monitored by time-resolved infrared-ultraviolet double resonance (IR-UV DR) spectroscopy. Rotational J-states associated with the (v1 + 3v 3) or (1 0 3 0 0)0 vibrational combination level, initially prepared by an IR pulse, are probed at ~299, ~296, or ~323 nm with UV laser-induced fluorescence via the A electronic state. The rovibrational J-states of interest belong to a congested manifold that is affected by anharmonic, l-resonance, and Coriolis couplings, yielding complex intramolecular dynamics. Consequently, collision-induced rovibrational satellites observed by IR-UV DR comprise not only regular even-?J features but also supposedly forbidden odd-?J features. A preceding paper (J. Phys. Chem. A 2003, 107, 10759) focused on low-J-value rovibrational levels of the 4vCH manifold (particularly those with J = 0 and J = 1) whereas this paper examines locally perturbed states at higher values of 7 (particularly J = 17 and 18, which display anomalous doublet structure in IR-absorption spectra). Three complementary forms of IR-UV DR experiments (IR-scanned, UV-scanned, and kinetic) are used to address the extent to which intramolecular perturbations influence the efficiency of J-resolved collision-induced energy transfer with both even and odd ?J. © 2005 American Chemical Society.

Original languageEnglish
Pages (from-to)8332-8343
Number of pages12
JournalJournal of Physical Chemistry B
Issue number17
Publication statusPublished - 5 May 2005


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