Journal of Chemical Physics, Vol.109, No.18, 7803-7809, 1998
The rotationally resolved infrared spectrum of the nu(1) stretch of the allyl radical
Transient infrared (IR) laser spectroscopy near 3100 cm(-1) was used to observe the v(1) and v(13) transitions of the allyl radical, with their band origins found to lie at 3113.9779(3) cm(-1) and near 3110.5 cm(-1), respectively. Detailed assignment and analysis of the v(1) transition identified over 1100 transitions, and yielded improved values for Delta(K) and Phi(K) ground state centrifugal distortion constants, as well as a new set of excited state (v(1) = 1) rotational and centrifugal distortion constants, in addition to determining the band origin. Transitions involving states with quantum number up to K-a = 11 and N = 27 were identified. Strong perturbations were found in the excited state, included global perturbations of the K-a' = 3 branch, extensive perturbations in the K-a' =2 and 4 branches, and very localized perturbations in the K-a' = 6 branch. The K-a' = 9 and 10 branches also appear to be significantly perturbed. Possible sources for these perturbations are discussed.