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Author Notes:

To whom correspondence should be addressed. E-mail: czako@chem.elte.hu. Present address: Laboratory of Molecular Structure and Dynamics, Institute of Chemistry, Eötvös University, H-1518, Budapest 112, P.O. Box 32, Hungary.

Author contributions: G.C. and J.M.B. designed research

G.C. performed research

G.C. analyzed data

G.C. and J.M.B. wrote the paper.

The authors thank Dr. Kopin Liu for sending the experimental data shown in Fig. 5.

The authors declare no conflict of interest.

Subject:

Research Funding:

The work was funded by the National Science Foundation (CHE-0625237) (to G.C.); the Scientific Research Fund of Hungary (OTKA, NK83583) (to G.C.); and the European Union and the European Social Fund (TÁMOP-4.2.1/B-09/1/KMR-2010-0003) (to G.C.); and the Department of Energy (DE-FG02-97ER14782) (to J.M.B.).

Keywords:

  • mode-specific dynamics
  • reactive scattering computations
  • state-to-state dynamics
  • permutationally invariant potential energy surfaces
  • benchmark ab initio data

Dynamics of the O(3P) + CHD3(vCH = 0,1) reactions on an accurate ab initio potential energy surface

Tools:

Journal Title:

Proceedings of the National Academy of Sciences

Volume:

Volume 109, Number 21

Publisher:

, Pages 7997-8001

Type of Work:

Article | Final Publisher PDF

Abstract:

Recent experimental and theoretical studies on the dynamics of the reactions of methane with F and Cl atoms have modified our understanding of mode-selective chemical reactivity. The O + methane reaction is also an important candidate to extend our knowledge on the rules of reactivity. Here, we report a unique full-dimensional ab initio potential energy surface for the O(3P) + methane reaction, which opens the door for accurate dynamics calculations using this surface. Quasiclassical trajectory calculations of the angular and vibrational distributions for the ground state and CH stretching excited O + CHD3(v1 = 0,1) → OH + CD3 reactions are in excellent agreement with the experiment. Our theory confirms what was proposed experimentally: The mechanistic origin of the vibrational enhancement is that the CH-stretching excitation enlarges the reactive cone of acceptance.

Copyright information:

© 2017 National Academy of Sciences.

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