Jiaxu Zhang, Li Yang, Diego Troya. Chemical Dynamics Simulations of the Hydroxyl Radical Reaction with Ethene[J]. Chinese Journal of Chemical Physics , 2013, 26(6): 765-773. doi: 10.1063/1674-0068/26/06/765-773
Citation: Jiaxu Zhang, Li Yang, Diego Troya. Chemical Dynamics Simulations of the Hydroxyl Radical Reaction with Ethene[J]. Chinese Journal of Chemical Physics , 2013, 26(6): 765-773. doi: 10.1063/1674-0068/26/06/765-773

Chemical Dynamics Simulations of the Hydroxyl Radical Reaction with Ethene

doi: 10.1063/1674-0068/26/06/765-773
Funds:  This work was supported by the National Science Foundation Grant (No.CHE-0547543), Air Force Office of Scientific Research Foundation Grant (No.FA9550-06-1-0165), and the Institute of Chemistry, Chinese Academy of Sciences (No.CMS-PY-201316)
  • We present a theoretical study of the reaction of the hydroxyl radical with ethene using electronic structure calculations and direct-dynamics simulations. High-accuracy electronic structure calculations at the CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVDZ level have been carried out to characterize the representative regions of the potential energy surface of various reaction pathways, including OH-addition and H-abstraction. These ab initio calculations have been employed to derive an improved set of parameters for the MSINDO semiempirical Hamiltonian specific to the OH+C2H4 reaction. The specific-reaction-parameter Hamilto-nian captures the ab initio data accurately, and has been used to perform direct quasiclas-sical trajectory simulations of the OH+C2H4 reaction at collision energies in the range of 2?10 kcal/mol. The calculated cross sections reveal that the OH-addition reaction domi-nates at all energies over H-abstraction. In addition, the excitation function of addition is reminiscent of a barrierless capture process, while that for abstraction corresponds to an activated one, and these trends can be connected to the transition-state energies of both reactions. We note that the development of an accurate semiempirical Hamiltonian for the OH+C2H4 reaction in this work required the inclusion of empirical dispersion corrections, which will be important in future applications for which long-range intermolecular attraction becomes significant
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Chemical Dynamics Simulations of the Hydroxyl Radical Reaction with Ethene

doi: 10.1063/1674-0068/26/06/765-773
Funds:  This work was supported by the National Science Foundation Grant (No.CHE-0547543), Air Force Office of Scientific Research Foundation Grant (No.FA9550-06-1-0165), and the Institute of Chemistry, Chinese Academy of Sciences (No.CMS-PY-201316)

Abstract: We present a theoretical study of the reaction of the hydroxyl radical with ethene using electronic structure calculations and direct-dynamics simulations. High-accuracy electronic structure calculations at the CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVDZ level have been carried out to characterize the representative regions of the potential energy surface of various reaction pathways, including OH-addition and H-abstraction. These ab initio calculations have been employed to derive an improved set of parameters for the MSINDO semiempirical Hamiltonian specific to the OH+C2H4 reaction. The specific-reaction-parameter Hamilto-nian captures the ab initio data accurately, and has been used to perform direct quasiclas-sical trajectory simulations of the OH+C2H4 reaction at collision energies in the range of 2?10 kcal/mol. The calculated cross sections reveal that the OH-addition reaction domi-nates at all energies over H-abstraction. In addition, the excitation function of addition is reminiscent of a barrierless capture process, while that for abstraction corresponds to an activated one, and these trends can be connected to the transition-state energies of both reactions. We note that the development of an accurate semiempirical Hamiltonian for the OH+C2H4 reaction in this work required the inclusion of empirical dispersion corrections, which will be important in future applications for which long-range intermolecular attraction becomes significant

Jiaxu Zhang, Li Yang, Diego Troya. Chemical Dynamics Simulations of the Hydroxyl Radical Reaction with Ethene[J]. Chinese Journal of Chemical Physics , 2013, 26(6): 765-773. doi: 10.1063/1674-0068/26/06/765-773
Citation: Jiaxu Zhang, Li Yang, Diego Troya. Chemical Dynamics Simulations of the Hydroxyl Radical Reaction with Ethene[J]. Chinese Journal of Chemical Physics , 2013, 26(6): 765-773. doi: 10.1063/1674-0068/26/06/765-773

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