Determination of absolute thermal rate constants for the charge-transfer reaction DBr[sup +]([sup 2]∏[sub I],v[sup +])+HBr→HBr[sup +]([sup 2]∏[sub I′],v′[sup +])+DBr

Xie, Jinchun; Zare, Richard N.
March 1992
Journal of Chemical Physics;3/15/1992, Vol. 96 Issue 6, p4293
Academic Journal
The charge transfer reaction DBr[sup +]([sup 2]∏[sub I],v[sup +],J[sup +])+HBr→HBr[sup +]([sup 2]∏[sub I′],v′[sup +],J′[sup +])+DBr is studied in a state-to-state manner under thermal conditions in a slowly flowing gas mixture of HBr and DBr. The DBr[sup +] reagent is prepared in a selected vibronic level by using (2+1) resonance-enhanced multiphoton ionization. The HBr[sup +] product is detected in a quantum-state-specific manner using laser-induced fluorescence. From the measurements of the molecular density and the populations of both HBr[sup +] product and DBr[sup +] reagent, the absolute thermal rate constants k(i,v[sup +]→i′,v′[sup +]) are determined for this charge-transfer process. The rate constants for near-resonant charge transfer in which Δv[sup +]=0 and Δi=0 are much large than charge-transfer channels in which either Δi≠0; the smallest rate constants are for those channels in which both Δi≠0 and Δv[sup +]≠0. The rotational distribution of the HBr[sup +](i′,v′[sup +]) products fits a temperature well in each case. For near-resonant charge transfer, the rotational temperature is slightly warmer than thermal, whereas for nonresonant charge transfer, the rotational temperature is much hotter than thermal. A model in which the excess energy of a charge-transfer process is statistically partitioned among all the degrees of freedom of the complex is able to predict closely the observed rotational temperature.


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