Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5415931 | Journal of Molecular Spectroscopy | 2007 | 8 Pages |
Abstract
We report fluorescence excitation and single vibronic level emission spectra of the AË1Aâ³âXË1Aâ² system of CDCl in the 500-740 nm region, measured under jet-cooled conditions using a pulsed discharge source. A total of 29 cold bands involving the pure bending levels 20n (n = 2-11), C-D stretching fundamental (101), and combination bands 20n301 (n = 2-10), 20n302 (n = 9), 10120n (n = 2-8), and 10120n301 (n = 7) were observed; most of these are reported here for the first time. Rotational analysis typically yielded band origins and rotational constants for both isotopomers (CD35Cl, CD37Cl). The derived AË1Aâ³ vibrational intervals are combined with previous studies at lower energy to determine excited state barriers to linearity for the 2n, 2n31, and 112n progressions. The AË1Aâ³ state C-D stretching frequency (2229.6 cmâ1) is determined here for the first time, in excellent agreement with ab initio theory. Following our observation of new bands in this system, we obtained single vibronic level (SVL) emission spectra which probe the vibrational structure of the XË1Aâ² state up to â¼8000 cmâ1 above the vibrationless level. The total number of XË1Aâ² and aË3Aâ³ levels observed is more than twice that previously reported, and a complete set of Dunham parameters was determined for the XË1Aâ² state of CD35Cl and CD37Cl. Comparisons with previous experimental and recent high level ab initio studies are reported. Our results shed new light on the vibrational structure of the XË1Aâ², AË1Aâ³, and aË3Aâ³ states of CDCl, and, more generally, spin-orbit coupling in the monohalocarbenes.
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Authors
Chong Tao, Calvin Mukarakate, Scott A. Reid,