The normal coordinate analysis of the allyl radical: calculation of the inertial defect and centrifugal distortion constants

The change in the centrifugal distortion constants of the allyl radical with the vibrational excitation to the ν 11 state was interpreted as being caused by the interaction of the ν 11 state with the overtone state of the ν 7 mode. This interpretation requires revision of the ν 7 frequency, in conformity with the recent results reported by Getty and co-workers (J. Am. Chem. Soc., 113 (1991) 801; Chem. Phys., 168 (1992) 357) using resonance Raman spectroscopy. The normal coordinate analysis was performed on the allyl radical based upon the vibrational assignment revised by Fjogstad and Ystenes (Spectrochim. Acta, Part A, 46 (1990) 47) and Getty and co-workers in order to calculate the inertial defect and centrifugal distortion constants for comparison with the observed values.