IDENTIFICATION OF OUT-OF-PLANE VIBRATIONS AND VIBRATIONAL POTENTIAL IN THE N-PI SINGLET OF PYRAZINE

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1974

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Ohio State University

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The out-of-plane vibrations in the first excited n-pi singlet of pyrazine shift to higher energies in the sequence: vapor < cyclohexane mixed crystal < benzene mixed crystal < pure crystal, and permit one to distinguish these modes from symmetric modes. The problem of the assignment of the out-of-plane vibrations in this state has been solved by means of the polarized absorption spectra of pyrazine in single crystals of benzene. A vibrational analysis has determined the vibronic coupling routes and the characteristics of the out-of-plane potential. Although the out-of-plane force constants are small, the molecule appears to be planar.

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Author Institution: Frick Chemical Laboratory, Princeton University; National Bureau of Standards, Princeton University

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