MODE SPECIFIC DYNAMICS IN THE PREDISSOCIATED, QUASILINEAR $B^{1}A^{\prime}$ STATE OF CHF PROBED BY OPTICAL-OPTICAL DOUBLE RESONANCE SPECTROSCOPY
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Date
2007
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Publisher
Ohio State University
Abstract
We have recently observed transitions to the predissociated, quasilinear $B^{1}A^{\prime}$ state of a halocarbene, CHF, using a fluorescence dip detected optical-optical double resonance technique via the $A^{1}A^{\prime\prime}$ state.} By exciting selected rotational levels in intermediate states belonging to the progressions 2$_0^{n}$, 1$_0^{1}$2$_0^{n}$, and $2_0^{n}$3$_0^{1}$, a variety of $B^{1}A^{\prime}$ state levels have been observed, extending to an energy of 7000 cm$^{-1}$ above the $B^{1}A^{\prime}$ state origin. In this talk, we will focus on the dynamics of the $B^{1}A^{\prime}$ state. All of the observed lines are predissociated, as evidenced by Lorentzian lineshapes, and the linewidths increase with increasing energy. A pronounced mode specificity is observed; levels containing CF stretching excitation dissociate more rapidly than nearly isoenergetic bending levels. The implications of these results for the dissociation mechanism will be emphasized.
Description
Author Institution: Department of Chemistry, Marquette University, Milwaukee, WI 53233; School of Chemistry, University of Sydney, NSW 2006, Australia