SINGLE QUANTUM-STATE RESOLVED COLLISION RELAXATION CROSS SECTION OF HIGHLY VIBRATIONALLY EXCITED SO$_2$ MEASURED BY KINETIC QUANTUM BEAT SPECTROSCOPY
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Date
2007
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Ohio State University
Abstract
The collision relaxation cross section of highly vibrationally excited SO$_2$ at energies around 45,000 $cm^{\-1}$, which is just below the dissociation limit, has been measured for several $\testit{single}$, highly vibrationally excited levels. The measurement was conducted on rotationally cooled SO$_2$ in supersonic jet condition using quantum beat spectroscopy. Quantum beat in laser induced fluorescence from the $\ {C}$ state is due to vibronic coupling between zero-order rovibronic levels of $\ {C}$ and $\ {X}$ states and can be analyzed to give the decay rate constants of the high vibrational levels of the $\ {X}$ state. It is found that the collision relaxation cross section of the single highly vibrationally excited level shows a strong correlation with the corresponding vibronic coupling matrix element, likely reflecting that the part of the vibrational character of the single high vibrational level that gives a larger coupling with the $\ {C}$ state also provide a stronger transition dipole moment contribution to its collision relaxation.
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Author Institution: Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104; Department of Chemistry, Temple University, Philadelphia,; PA 19122