Time-Resolved Rotational Energy Transfer and Spectral Line Broadening in Acetylene. a High Resolution Raman Study.

Domenech, J. L.; Martinez, R. Z.; Bermejo, D.
Referencia bibliográfica

"International Symposium On Molecular Spectroscopy, 65th Meeting, Held 21-25 June, 2010 at Ohio State University. http://molspect.chemistry.ohio-state.edu/symposium_65/symposium/"

Fecha de publicación:
6
2010
Número de autores
3
Número de autores del IAC
0
Número de citas
0
Número de citas referidas
0
Descripción
The quasi-cw stimulated Raman technique is a powerful tool for the determination of collisional broadening and line-mixing parameters, which bear a very direct relationship with the rotational energy transfer rate constants matrix at the state-to-state level. Indeed, the broadening coefficients and the analysis of line-mixing profiles, frequently combined with a rate-law analysis, have provided a wealth of information on collision physics for many gas systems throughout the years. We report on new high resolution measurements of the broadening coefficients on the Q-branch of the ν_2 band of acetylene. Furthermore, last year at this meeting, we reported on a new technique for the determination of state-to-state rotational energy transfer rate constants. based on a time-resolved double-resonance Raman-Raman scheme. It uses the quasi-continuous stimulated Raman-loss technique for the probe stage. Through a systematic recording of the time evolution of rotational populations from a single initially pupulated J level, it allows the direct determination of most elements of the rate-constant matrix without resorting to fitting or scaling laws. The comparison of the results obtained from from the high resolution spectroscopic approach with those from the time-resolved dynamics experiment provides insight into the collision mechanisms and some of the assumptions or simplifications usually made in rate-law analysis.