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Direct determination of state-to-state rotational energy transfer rate constants via a Raman-Raman double resonance technique: ortho-acetylene in v2=1 at 155 K

AutorDoménech, José Luis ; Martínez, Raúl Z. ; Ramos, Ángel ; Bermejo, Dionisio
Palabras claveEndor
Excited states
Organic compounds
Rotational states
Stimulated Raman scattering
Vibrational states
Fecha de publicación15-abr-2010
EditorAmerican Institute of Physics
CitaciónJournal of Chemical Physics 132, 154303 (2010)
ResumenA new technique for the direct determination of state-to-state rotational energy transfer rate constants in the gas phase is presented. It is based on two sequential stimulated Raman processes: the first one prepares the sample in a single rotational state of an excited vibrational level, and the second one, using the high resolution quasi-continuous stimulated Raman-loss technique, monitors the transfer of population to other rotational states of the same vibrational level as a function of the delay between the pump and the probe stages. The technique is applied to the odd-J rotational states of v2 = 1 acetylene at 155 K. The experimental layout, data acquisition, retrieval procedures, and numerical treatment are described. The quantity and quality of the data are high enough to allow a direct determination of the state-to-state rate constant matrix from a fit of the experimental data, with the only conditions of detailed balance and of a closed number of states. The matrix obtained from this direct fit is also compared with those obtained using some common fitting and scaling laws.
Descripción12 pages, 6 figures, 4 tables.- PACS nrs: 33.20.Sn, 33.15.Mt, 33.20.Fb, 33.40.+f, 33.20.Tp, 33.80.Wz.
Versión del editorhttp://dx.doi.org/10.1063/1.3374031
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