Jet-cooled laser-induced fluorescence spectroscopy of methylcyclohexoxy radicals

Abstract

Cyclohexoxy and its methyl substituted variants play an important role in atmospheric chemistry. Direct spectral observation of these radicals can provide information about their structures and serve as convenient diagnostics for their monitoring. In this work, we report the first time observation of the LIF spectra of 2-, 3-, and 4-methylcyclohexoxy radicals in supersonic jet-cooled conditions. All spectra are consistent with a single conformer, and thermodynamic analysis of the conformers suggests that the conformer has the diequatorial (e, e) chair structure. Vibrational frequency analysis was performed using CASSCF/6-31+G(d) method on the state of radicals and the vibronic bands were assigned. The origin band of the methyl substituted cyclohexoxy shifted to red with the decrease of the separation distance between the methyl group and the oxygen atom on the ring. Different spectral character of 2-methylcyclohexoxy radical suggested that the neighboring methyl group affected the behavior of the radical on the excited state.