On intensity perturbations in vibronically induced radiative transitions
- 1 April 1975
- journal article
- research article
- Published by Taylor & Francis in Molecular Physics
- Vol. 29 (4) , 1063-1072
- https://doi.org/10.1080/00268977500100901
Abstract
Intensity perturbations in forbidden radiative transitions due to cubic anharmonic mixing involving the inducing mode and a totally symmetric progression-forming mode are discussed. It is shown that such mixing will lead to deviations from mirror symmetry of the absorption and fluorescence structure because the destructive-constructive interference pattern which prevails in absorption is different to that in emission. This analysis is applied to intensities in the 2600 Å system of benzene. Moderate cubic coupling energies (ca. 10 cm-1) have marked effects on intensity distributions even when the interacting levels are 200 cm-1 apart. The splitting of the progressions 10 n 61 2 and 1 n 062 1 into two sub-progressions (l=0, 2) is linearly dependent on the extent of vibronic excitation in the a 1g mode v 1. These effects are amenable to experimental detection.Keywords
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