ELECTRIC FIELD INDUCED PERTURBATIONS IN OPTICAL SPECTROSCOPY

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1972

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Ohio State University

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It has long been known that application of an external electric field can mix two electronic states if there exists a non zero component of the transition moment matrix element between the two states, and if they lie close enough in energy. It is shown how this effect can be useful in identifying and characterizing electronic states which can not normally be observed spectroscopically. Field induced perturbations are observed in the $\Pi ^ * \leftarrow \Pi $ transitions in benzonitrile and aniline. These observations indicate the existence of previously unidentified states in these molecules and we are able to determine their vibronic symmetry ( $B_{2}$ in both cases). In addition, by analysis of the non-linear effects we are able to determine the zero field energy and dipole moments of the states as well as their transition moment with respect to the previously observed states.

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Author Institution: Department of Chemistry, University of Illinois Urbana

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