$n\pi^{*}$ TRANSITIONS IN SULFUR DERIVATIVES OF TETRAMETHYL-1,3-CYCLOBUTANEDIONE

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1980

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Ohio State University

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The polarized low-temperature crystal absorption spectra of tetramethyl-1,3-cyclobutanedithione–h12 and d12 (II) have been measured in the visible region, and nπ excited states identified as follows :3Au with origin (h12/d12) at 16829/16836 cm−11Au and 1B1g with nearly degenerate origins near 18000cm−1 and probably 1Au and 1B1g near 19500cm−1. The singlet excited states lie close together and perturb each other strongly. Isotope shifts, and anologies to the spectrum of the dione (I)1, played an important part in the analysis. As in the dione (I), CH/CD stretching vibrations in the peripheral methyl are groups are active in intensity borrowing, and the effects of excitation are delocalized over the entire molecule. Preliminary results for the C2v molecule (III) will also be presented. [Figure]

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1R. D. Gordon, M. Caris, and D. G. Newman, J. Mol. Spectrosc. 60, 130-149 (1976).


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