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 nu11 state was interpreted as being caused by the interaction of the nu11 state with the overtone state of the nu7 mode. This interpretation requires revision of the nu7 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.