Rotationally resolved jet-cooled and room temperature spectra of the ν3 stretch of vinoxy radical (CH2CHO) have been obtained near 2800 cm−1 by means of tunable infrared laser spectroscopy. About 500 transitions corresponding to b-type selection rules have been assigned in the jet-cooled spectrum recorded in the region 2809–2860 cm−1. The band origin has been determined to be 2827.913 cm−1. A number of lines are split into doublets by the electron spin–rotation interaction. The jet-cooled spectrum has been supplemented by transitions with high N or K values observed in the room temperature spectrum, which was recorded over the spectral region 2754–2894 cm−1. Both local and global perturbations have been found in the upper state energy levels. Least-squares fitting of the apparently unperturbed levels yielded molecular constants as well as centrifugal distortion and spin-rotational constants for the upper state.
The high-resolution infrared spectrum of jet-cooled methoxy radical (CH3O) in the region 2850–2940 cm−1 has been recorded at about 26 K in a pulsed slit-jet expansion producing the radical by excimer laser flash photolysis. A perpendicular band centered near 2885 cm−1 was assigned to a portion of the C-H asymmetric stretch vibration (ν4) of CH3O by means of ground-state combination differences. Five ΔP=+1 subbands with P″=−1.5, −0.5, 0.5, 1.5, 2.5, and J″ up to 9.5 have been assigned. Because of the low jet temperature, the assigned transitions all arise from the ground E3/2 fine-structure component of the lowest vibronic state. Preliminary analysis yields values of A, B, and D of 5.232(12), 0.913(8), and 2.5(1.5)×10−5 cm−1, respectively. A small hyperfine splitting was observed in the P″=0.5 series transitions.
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