Dispersed fluorescence spectroscopy of excited rovibrational states in S formaldehyde
- 1 October 1995
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 103 (13), 5279-5289
- https://doi.org/10.1063/1.470564
Abstract
Dispersed fluorescence (DF) spectroscopy is used to explore the rovibrational structure of highly excited S0 formaldehyde (H2CO). A narrowband laser excites formaldehyde molecules to a single S1 rovibronic quantum state, and the resulting fluorescence is dispersed with a monochromator. DF spectra of ten vibrational levels with excitation in ν2, the carbon–oxygen stretch, and ν4, the out‐of‐plane bend, have been recorded, and the effective A, B, and C rotational constants are extracted. Five of the effective A rotational constants and seven of the effective B and C rotational constants are new to the literature. The dependence of these effective rotational constants on vibrational state are both calculated and discussed with regard to both the present and previous experiments. Particular attention is given to the manner in which that the effective A rotational constant depends on increasing excitation in ν4 due to the strong A‐axis ν4/ν6 Coriolis interaction. For states where v2 is less than two, quantitatively accurate values for the nonlinear dependence of the A rotational constant on quanta in ν2 and ν4 is achieved by a simultaneous consideration of the strong A‐axis ν4/ν6 Coriolis interaction and the 11↔42, 11↔62, and 51↔2161 Fermi interactions.Keywords
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