Collisional energy transfer in CH3 radical decomposition—experiment versus theory

文献情報

出版日 2002-08-02

DOI 10.1039/B110267M

インパクトファクター 3.676

著者

E. Goos, H. Hippler, C. Kachiani, H. Svedung

原文を見る

要旨

Experimentally determined incubation times in the thermal decomposition of methyl radicals were used to obtain collisional energy transfer probability information by adopting a discrete vibrational energy level master-equation scheme with specific rate constants from the statistical adiabatic channel model. The agreement with information from classical molecular dynamic, MD, simulations of CH3–Ar collisions was shown to be remarkably good. Results from MD simulations also support the assumption of thermally equilibrated rotations used here and in earlier work. The sensitivity of the pressure fall-off behaviour of the decomposition channels to remaining uncertainties in the energy transfer profiles is shown to be significant, in this case, as a consequence of the large number of collisions needed to reach activation. Nevertheless, we find classical molecular dynamics simulation to be useful and a good starting point in obtaining the collisional energy transfer kernel to be used in master-equation calculations treating the most obvious quantum effects through the use of discrete energy levels at low energies.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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