The fluorescence excitation spectrum of chromyl chloride (CrO2Cl2) cooled in a free jet expansion

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Abstract
The fluorescence excitation spectrum of CrO2Cl2 in a free jet has been studied using a single mode tunable CW dye laser. Spectra were recorded for the A4 (origin), A5, and D5 bands. Sequence congestion has been entirely eliminated and detailed rotational structure of the bands observed for the first time. Assignment of the A4 origin band indicates the excited state to be B1 in vibronic symmetry under the C2v point group. The best least squares fit rotational constants are: A″=0.1073±0.0002 (cm−1); A′=0.0910±0.0003 (cm−1), B″=0.0620±0.0004 (cm−1); B′=0.0659+0.0003 (cm−1); C″=0.0521±0.0010 (cm−1); C′=0.0524±0.0010 (cm−1). Assignment of the D5 band indicates it is based on the same electronic transition but involves a symmetric vibration in the excited state. Possible geometries for the ground and excited states are also reported.