Vibronic analysis of the à 2A1–X̃ 2E laser-induced fluorescence of jet-cooled CH3S

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Abstract
The methylthio (CH3S) radical has been formed by KrF laser photolysis of dimethyl disulfide (CH3SSCH3) in a free‐jet expansion. The à 2A1←X̃ 2E laser‐induced fluorescence excitation spectrum was obtained in the wavelength region 350–382 nm. The origin lies at 26 526.3 cm−1 and the spin–orbital splitting for X̃ (2E3/2 and 2E1/2)was determined to be −259.1 cm−1. Several progressions indicated that ν’2=1098±2,ν3=401±2 cm−1, and (with less certainty) ν’6=635±10 cm−1. The predissociation threshold was estimated to be slightly above 28 016 cm−1, ∼1490 cm−1 above the v’=0 level of the à state. The dispersed fluorescence was observed in the 363–530 nm region. The main progressions give ν■2=1313±5 cm−1, ν‘3=727±3 cm−1, and ν■5=1496±6 cm−1. Weaker lines are also consistent with some possible vibrational frequencies ν‘1=2776 cm−1, ν■4=2706 cm−1, and ν‘6=586 cm−1.

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