Article
Effects of CH stretch excitation on the H+CH4 reaction.
Department of Chemistry, Stanford University, Stanford, California 943055080, USA.
The Journal of Chemical Physics
(Impact Factor: 3.12).
11/2005;
123(13):134301.
DOI: 10.1063/1.2034507
Source: PubMed

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ABSTRACT: Sevendimensional timedependent wave packet calculations have been carried out for the title reaction to obtain reaction probabilities and cross sections for CHD3 in J0 = 1, 2 rotationally excited initial states with k0 = 0  J0 (the projection of CHD3 rotational angular momentum on its C3 axis). Under the centrifugal sudden (CS) approximation, the initial states with the projection of the total angular momentum on the body fixed axis (K0) equal to k0 are found to be much more reactive, indicating strong dependence of reactivity on the orientation of the reagent CHD3 with respect to the relative velocity between the reagents H and CHD3. However, at the coupledchannel (CC) level this dependence becomes much weak although in general the K0 specified cross sections for the K0 = k0 initial states remain primary to the overall cross sections, implying the Coriolis coupling is important to the dynamics of the reaction. The calculated CS and CC integral cross sections obtained after K0 averaging for the J0 = 1, 2 initial states with all different k0 are essentially identical to the corresponding CS and CC results for the J0 = 0 initial state, meaning that the initial rotational excitation of CHD3 up to J0 = 2, regardless of its initial k0, does not have any effect on the total cross sections for the title reaction, and the errors introduced by the CS approximation on integral cross sections for the rotationally excited J0 = 1, 2 initial states are the same as those for the J0 = 0 initial state.The Journal of Chemical Physics 10/2014; 141(14):144309. DOI:10.1063/1.4897308 · 3.12 Impact Factor 
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ABSTRACT: By exciting the rotational modes of vibrationally excited CHD3(v1 = 1, JK), the reactivity for the Cl + CHD3 → HCl + CD3 reaction is observed enhanced by as much as a factor of two relative to the rotationless reactant. To understand the mode specificity, the reaction dynamics was studied using both a reduceddimensional quantum dynamical model and the conventional quasiclassical trajectory method, both of which reproduced qualitatively the measured enhancements. The mechanism of enhancement was analyzed using a FranckCondon model and by inspecting trajectories. It is shown that the higher reactivity for higher J states of CHD3 with K = 0 can be attributed to the enlargement of the cone of acceptance. On the other hand, the less pronounced enhancement for the higher J = K states is apparently due to the fact that the rotation along the CH bond is less effective in opening up the cone of acceptance.The Journal of Chemical Physics 08/2014; 141(7):074310. DOI:10.1063/1.4892598 · 3.12 Impact Factor 
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ABSTRACT: A global potential energy surface (PES) for the H+CH4 <> H2+CH3 reaction has been constructed using the neural networks method based on 47783 high level ab initio geometry points. Extensive quasiclassical trajectories and quantum scattering calculations were carried out to check the convergence of the PES. This PES, fully converged with respect to the fitting procedure and the number of ab initio points, has a very small fitting error, and is much faster on evaluation than the modified Shepard interpolating PES, representing the best available PES for this benchmark polyatomic system.Chinese journal of chemical physics 08/2014; 27(44):373379. DOI:10.1063/16740068/27/04/373379 · 0.72 Impact Factor
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