- 作者: Frank Budenholzer and Po-Shen Lin
- 中文摘要:
Department of Chemistry, Fu Jen Catholic University, Hsinchuang 242, Taiwan, R.O.C.
Classical trajectories have been calculated for the unimolecular dissociation reaction H(D)FCO R H(D)F + CO over a modified form of the electronic ground state potential surface of Wei and Wyatt [J. Phys. Chem. 1993, 97, 13580]. The modifications of the potential energy surface and the method of calculating the trajectories are described in an earlier publication from our laboratory [J. Phys. Chem. A. 1998, 102, 947]. Trajectories were initiated with the classical zero point energy distributed randomly in the six normal modes of the molecule and an additional approximately 60 kcal/mol distributed in one of the six normal modes. Clear evidence of mode specificity was found in that the excitation of the six different modes leads to significantly different rates of reaction: CH stretch > CH bend @ CF stretch >> CO stretch @ FCO bend > out of plane bend. For DFCO, mode specificity is considerably less apparent in that the range of lifetimes for the six normal modes is less than half that for HFCO. Average product CO and HF distributions were also determined for both HFCO and DFCO dissociation. To investigate the degree of IVR between various modes, trajectories were calculated with the same initial energy approximately equally divided between two different initial modes. Finally, trajectories were calculated to study the effect of increasing rotational energy on the rate of HFCO dissociation. These results are discussed in terms of general theories of reaction rates, recent theoretical treatments of HFCO dissociation and experimental results. - 英文摘要: --
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