ON THE IMPORTANCE OF FRANCK- CONDON FACTORS IN SECOND-ORDER SPIN-ORBIT COUPLING: ISOTOPE EFFECT ON THE FINE-STRUCTURE PARAMETERS OF $^{3}(n\pi^{*})$ BENZOPHENONES
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Date
1979
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Ohio State University
Abstract
Isotope effects on the fine-structure parameters of $^{3}(n\pi^{*})$ benzophenones containing $^{1}H,\ ^{2}H,\ ^{12}C,\ ^{13}C,\ ^{16}O$, and $^{18}O$ nuclei have been examined by zero-field optically-detected magnetic resonance (zf-ODMR) spectroscopy. A portion of these results have recently been reported by Hochstrasser, Scott and $Zewail.^{1}$ The changes produced by $^{2} H$ and $^{13}C$ substitution are different in magnitude and opposite in sign, those produced by $^{13}C$ and $^{18}O$ substitution are similar in magnitude as well as sign, and those produced by simultaneous $^{2}H$ and $^{13}C$ substitution are additive. Concomitant changes are observed in the phosphorescence spectra of these species. A comparison of the data provides direct experimental evidence for the importance of Franck-Condon factors in determining the extent to which the lowest triplet state is mixed with nearby states via the spin-orbit interaction.
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$^{1}$R. M. Hochstrasser, G. W. Scott and A. H. Zewail, Mol. Phys. 36, 475 (1978).
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