SPECTACULARLY INTENSE INFRARED VIBRATIONAL TRANSITIONS IN SPATIALLY DEGENERATE ELECTRONIC STATES
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Date
1985
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Ohio State University
Abstract
High symmetry for molecules in non-degenerate electronic states tends to reduce or eliminate the possibilities for electric dipole transitions in polyatomic molecules. However if the electronic state is degenerate, Child and Longuet-Higgios showed 25 years ago, that new transitions can occur in both the microwave and IR region. We have extended this early work and found various types of spectacularly intense vibrational transitions, with oscillator strengths comparable to fully allowed electronic transitions. The close connection between the intensity of these enhanced vibrational transitions and the existence of an anomalous permanent dipole moment, with its implications for microwave spectra and the Stark effect, is elucidated. These results are of special interest for experiments aimed at detecting the spectra of small, symmetrical polyatomic ions and radicals.
Description
Author Institution: Department of Chemistry, The Ohio State University; Department of Chemistry, Ben-Gurion University of the Negev; Department of Chemistry, The Ohio State University