THE PERFLUORO EFFECT ON THE MOLECULAR RYDBERG STATES OF BROMO- AND IODOETHYLENE

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1976

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Ohio State University

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In comparing the vacuum ultraviolet spectra of bromo- and iodoethylene with the spectra of their perfluoro analogues, it is noted that many of the absorptions are shifted in energy. Fluorine substitution has been found to stabilize the $\sigma$ systems and increase the term values of $(\Pi, ns)$ Rydberg transition, but to have little effect on $\Pi$ ionization potentials or p Rydberg term $values.^{1}$ However, in these compounds, there are two $(\Pi, np)$ Rydberg series assigned and the term values of one series, believed to be associated with in-plane p Rydberg orbitals, showed a marked increase with fluorination. Additional substituent effects on band intensities and halogen-$\Pi$ system interaction parameters have also been observed and are discussed.

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$^{1}$M. B. Robin, ``Higher Excited States of Polyatomic Molecules,'' Academic Press, New York, 1974. This work was supported by the Robert A. Welch Foundation.
Author Institution: Department of Chemistry, North Texas State University

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