Higher Vibrational Levels of the A{}^1Π_u State of C{}_3 Observed by Laser-Induced Fluorescence

Details Higher Vibrational Levels of the A{}^1Π_u State of C{}_3 Observed by Laser-Induced Fluorescence Higher Vibrational Levels of the A{}^1Π_u State of C{}_3 Observed by Laser-Induced Fluorescence

Jun 2010

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2010mss..confemi09c&link_type=abstract

"International Symposium On Molecular Spectroscopy, 65th Meeting, Held 21-25 June, 2010 at Ohio State University. http://molspec

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Radicals And Ions

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The vibrational structure of the A{}^1Π_u electronic state of C{}_3 in the region 26000-31000 cm{}-1 has been re-examined, using laser excitation spectra of jet-cooled molecules. Rotational constants and vibrational energies have been determined for over 60 previously unreported vibronic levels; a number of other levels have been re-assigned. The vibrational structure is complicated by interactions between levels of the upper and lower Born-Oppenheimer components of the A{}^1Π_u state, and by the effects of the double minimum potential in the Q_3 coordinate, recognized by Izuha and Yamanouchi. The present work shows that there is also strong anharmonic resonance between the overtones of the ν_1 and ν_3 vibrations. For instance, the Σ^+_u vibronic levels 2 1{}^+1 and 0 1{}^+3 are nearly degenerate in zero order, but as a result of the resonance they give rise to two levels 139 cm{}-1 apart, centered about the expected position of the 2 1{}^+1 level. Similarly, the 202 level lies 60 cm{}-1 lower than expected because of interaction with the 400 and 004 levels. With these irregularities recognized, every observed vibrational level up to 29550 cm{}-1 (a vibrational energy of nearly 5000 cm{}-1) can now be assigned.
M. Izuha and K. Yamanouchi, J. Chem. Phys. 109, 1818 (1998).

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