The CaCCHÃ2Π–X̃2Σ+522and 520Bands Studied by High Resolution Spectroscopy: The Ca–C–C Bending Vibration and Vibronic Interaction
✍ Scribed by Mingguang Li; John A. Coxon
- Publisher
- Elsevier Science
- Year
- 1997
- Tongue
- English
- Weight
- 541 KB
- Volume
- 183
- Category
- Article
- ISSN
- 0022-2852
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✦ Synopsis
The CaCCH 5 2 2 and 5 0 2 bands in the A ˜2P -X ˜2S / system, involving the excited Ca-C-C bending vibrations, have been rotationally analyzed via CW dye laser excitation and dispersed fluorescence with a CCD array detector. The A ˜2P £ 5 Å 2 level is subject to Renner -Teller and spin-orbit splittings; in addition, K-resonance interactions are observed between the nearby 2 F and 2 P vibronic components. With a full matrix treatment of the six vibronic components (k 2 P, m 2 P, and 2 F ) in the upper state, the line positions of the six subbands of the 5 2 2 band were fitted simultaneously by least squares. The three higher vibronic components, especially the k 2 P 1 /2 component, were found to be perturbed strongly by the lower vibronic components of the £ 5 Å 3 level. This perturbation has been analyzed by means of second-order perturbation theory involving the B ˜2S / electronic state and results in an estimate of the dipolar vibronic interaction parameter, e ( 2) 5 v 5 Å 08.31 cm 01 . The 5 0 2 band was studied through dispersed fluorescence and served to establish an accurate energy of the £ 5 Å 2 vibrational level relative to the zero-point vibration level in both the A ˜and X ˜states.