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Single vibronic level fluorescence and relaxation spectra of s-tetrazine-d0 and d2 vapors
Authors:Donald V. Brumbaugh  K.K. Innes
Affiliation:Department of Chemistry, State University of New York, Binghamton, NY 13901, USA
Abstract:The third strongest cold band in the 5500Å absorption spectrum of s-tetrazine vapor is assigned to 6b02 by analysis of single-vibronic-level (SVL) fluorescence spectra obtained with a tunable cw dye laser. Fermi resonance model calculations for the doublet 6a01…6b02 simulate the perturbations of relative intensities in ν6a fluorescence progressions which arise fron interference between the two terms of the Franck-Condon factors. Addition of a quartic anharmonic term to the quadratic ν6b potential accounts for the observed spacing of the observed 6b1 and 6b2 levels and suggests a likely candidate for the heretofore missing 6b04 member of the Fermi resonance triad. Weak bands with in-plane polarization are revealed in fluorescence and contribute to a list of newly measured frequencies of the ground state. Experiments with added n-pentane show that rotational relaxation proceeds at the hard-sphere rate while vibrational relaxation is about five times slower. Vibrational relaxation exhibits non-statistical distribution in the early stages; it is rather distinctive when starting from the zero-level of the excited state, but is reminiscent of earlier work (on benzene) when starting from the 16b1 level. Identification of the level 6b1 is supported by these relaxation experiments.
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