Electronic Spectra of the Heteroisotopic CH2D and CHD2 Radicals by Resonance Enhanced Multiphoton Ionization.

The 3p 2B1←←X 2B1 bands of CH2D and CHD2 radicals were observed between 305 and 335 nm by mass resolved, 2+1 resonance enhanced multiphoton ionization spectroscopy. Spectroscopic constants were found for the 3p 2B1 Rydberg state of the CH2D radical (ν00=59 940 cm−1, ν1a1 CH2 stretch=2995 cm−1, ν2a1 CD stretch=2220 cm−1, ν4b1 out‐of‐plane large amplitude (OPLA)=1260 cm−1, ν5b2 CH2 asymmetric stretch=3055 cm−1, ν6b2 CD bend=1115 cm−1) and of the CHD2 radical (ν00=59 920 cm−1, ν1a1 CH stretch=3040 cm−1, ν2a1 CD2 stretch=2150 cm−1, ν4b1 OPLA=1165 cm−1, ν6b2 CH bend=1210 cm−1). Vibrational frequencies calculated by ab initio theory agree well with the experimental data.