ROTATIONALLY RESOLVED PHOSPHORESCENCE EXCITATION SPECTRUM OF p-RENZOQUINONE IN A SUPERSONIC JET. ORBITAL SYMMETRY OF THE LOWEST TRIPLET STATE

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1988

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Ohio State University

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Abstract

We report the first study of the lowest triplet state of p-benzoquinone (pBQ) with both vibrational and rotational resolution, using the technique of phosphorescence excitation spectroscopy in a supersonic jet. The strongest band in the spectrum, at ca. 535 nm has previously been assigned as the origin of the $^{3}A_{u} \leftarrow {^{1}}A_{g}$ electronic transition.1 The rotational structure of this band will be presented and shown to be inconsistent with assignment of $A_{u}$ orbital symmetry to the lowest triplet state. A resolution of this problem will be proposed, leading to a mutually consistent interpretation of the properties of triplet pBQ in the gas and condensed phase, and its geometry, vibrational frequencies, and electronic character.

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$^{\ast}$ Work supported by NSF. $^{1}$ Hollas, J. M., Spectrochim. Acta 20, 1563 (1964).
Author Institution: Department of Chemistry, University of Pittsburgh

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