ELECTRONIC SPECTRA OF THE HETEROISOTOPIC $CH_{2} D$ AND $CD_{2} H$ RADICALS

Author Institution: Chemical Kinetics and Thermodynamics Division, Chemical Science and Technology Laboratory, National Institute of Standards and TechnologyThe $3p ^{2}B_{1} \leftarrow \leftarrow \widetilde{X}^{2}B_{1}$ bands of $CH_{2}D$ and $CHD_{2}$ radicals were observed between 305 and 335 nm by mass resolved 2 + 1 resonance enhanced multiphoton ionization(REMP1) spectroscopy. Spectroscopic constants were found for the $3_{p} ^{2}B_{1}$ Rydberg state of the $CH_{2}D$ radical $(\nu_{00}=59940 cm^{-1}, \nu_{1} a_{1} CH_{2}$ stretch=$2995 cm^{-1}, \nu_{2} a_{1} $CD stretch=$2220 cm^{-1}, \nu_{4} b_{1} OPLA = 1260 cm^{-1}, \nu_{3} b_{2} CH_{2}$ asym stretch = $3055 cm^{-1}, \nu_{6} b_{2} $CD bend = $115 cm^{-1}$) and of the $CHD_{2}$ radical $(\nu_{00} = 59920 cm^{-1}, \nu_{1} a_{1} $CH stretch = $3040 cm^{-1}, \nu_{2} a_{1} CD_{2}$ stretch = $2150 cm^{-1}, \nu_{4} b_{1}$ OPLA = $1165 cm^{-1}, \nu_{6} b_{2} $CH bend =$1210 cm^{-1})$. Vibrational frequencies calculated by {ab initio} theory agree well with the experimental data