THE MULTIPHOTON IONIZATION SPECTRA OF TRI-ETHYLENED IAMINE AND QUINUCLIDINE

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1977

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Ohio State University

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The gas-phase multiphoton ionization spectra of triethylenediamine (DAECO) and quinuclidine (ABCO) have been measured. These rigid, symmetric $(D_{3h}$ and $C_{3v}$, respectively) caged amines provide excellent models for intramolecular through-space and through-bond orbital interactions. A wide spectral range of 20 000 $cm^{-1}$ has been studied, and three lowest energy molecular Rydberg states (DABCO) have been found as two-photon resonances in the three and four-photon ionization spectrum. Two of these resonances $(S_{1}$ and $S_{3})$ have not been observed in conventional one-photon spectra, while the third $(S_{2})$ resonance appears in exactly the same spectral position, with the same vibronic structure, as a previously reported one-photon resonance. Symmetry selection rules along with published photoelectron and fluorescence results are utilized to propose new assignments for these low-lying states.

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Author Institution: Department of Chemistry, University o California

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