Collisional relaxation of single rotational states in highly vibrationally excited acetylene

The combination of vibrational overtone excitation with time-resolved laser induced fluorescence detection of the excited molecule permits the study of collisional energy transfer in highly vibrationally excited molecules with single quantum state resolution. We apply this new technique to aceytlene...

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Bibliographic Details
Published in:The Journal of chemical physics 1988-05, Vol.88 (9), p.5976-5978
Main Authors: CARRASQUILLO, E, UTZ, A. L, CRIM, F. F
Format: Article
Language:English
Subjects:
Atomic and molecular collision processes and interactions
Atomic and molecular physics
Exact sciences and technology
Physics
Scattering of atoms, molecules and ions
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Summary:The combination of vibrational overtone excitation with time-resolved laser induced fluorescence detection of the excited molecule permits the study of collisional energy transfer in highly vibrationally excited molecules with single quantum state resolution. We apply this new technique to aceytlene excited in the region of the second CH stretching overtone transition (3νCH) (εvib =9640 cm−1) and probed via the à electronic state. Our results show that self-relaxation proceeds at essentially the gas kinetic collision rate while quenching by the rare gases He, Ar, and Xe is only about a factor of two slower. The insensitivity of the relaxation rate to the structure of the collision partner clearly points to rotational relaxation or intramolecular vibrational energy transfer as the mechanism for collisionally depopulating the initially prepared state.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.454512