A new full-dimensional potential energy surface for the title reaction has been constructed using the modified Shepard interpolation scheme. Energies and derivatives were calculated using the UCCSD(T) method with aug-cc-pVTZ and 6-311++G(3df,2pd) basis sets, respectively. A total number of 30 000 data points were selected from a huge number of molecular configurations sampled by trajectory method. Quantum dynamical calculations showed that the potential energy surface is well converged for the number of data points for collision energy up to 2.5 eV. Total reaction probabilities and integral cross sections were calculated on the present surface, as well as on the ZBB3 and EG-2008 surfaces for the title reaction. Satisfactory agreements were achieved between the present and the ZBB3 potential energy surfaces, indicating we are approaching the final stage to obtain a global potential energy surface of quantitative accuracy for this benchmark polyatomic system. Our calculations also showed that the EG-2008 surface is less accurate than the present and ZBB3 surfaces, particularly in high energy region.
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14 February 2011
Research Article|
February 14 2011
Ab initio potential energy surface and quantum dynamics for the H + CH4 → H2 + CH3 reaction
Yong Zhou;
Yong Zhou
1State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences
, Dalian 116023, People's Republic of China
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Bina Fu;
Bina Fu
1State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences
, Dalian 116023, People's Republic of China
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Chunrui Wang;
Chunrui Wang
1State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences
, Dalian 116023, People's Republic of China
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Michael A. Collins;
Michael A. Collins
2Research School of Chemistry,
Australian National University
, Canberra, ACT 0200, Australia
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Dong H. Zhang
Dong H. Zhang
a)
1State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences
, Dalian 116023, People's Republic of China
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Yong Zhou
1
Bina Fu
1
Chunrui Wang
1
Michael A. Collins
2
Dong H. Zhang
1,a)
1State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences
, Dalian 116023, People's Republic of China
2Research School of Chemistry,
Australian National University
, Canberra, ACT 0200, Australia
a)
Electronic mail: [email protected].
J. Chem. Phys. 134, 064323 (2011)
Article history
Received:
December 08 2010
Accepted:
January 14 2011
Citation
Yong Zhou, Bina Fu, Chunrui Wang, Michael A. Collins, Dong H. Zhang; Ab initio potential energy surface and quantum dynamics for the H + CH4 → H2 + CH3 reaction. J. Chem. Phys. 14 February 2011; 134 (6): 064323. https://doi.org/10.1063/1.3552088
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