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Journal of Chemical Physics / Volume 132 / Issue 8 / ARTICLES / Theoretical Methods and Algorithms

J. Chem. Phys. 132, 084103 (2010); http://dx.doi.org/10.1063/1.3304920 (10 pages)

Quantum dynamics of the H+CH4→H2+CH3 reaction in curvilinear coordinates: Full-dimensional and reduced dimensional calculations of reaction rates

Gerd Schiffel and Uwe Manthe

Theoretische Chemie, Fakultät für Chemie, Universität Bielefeld, Postfach 100131, D-33501 Bielefeld, Germany

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(Received 25 November 2009; accepted 13 January 2010; published online 23 February 2010)

Full-dimensional quantum dynamics calculations for the H+CH4→H2+CH3 reaction using curvilinear coordinates are presented. A curvilinear coordinate system to describe reactions of the type X+YCH3→XY+CH3 is developed which facilitates efficient calculations using the multiconfigurational time-dependent Hartree (MCTDH) approach. To describe the bending motion of the X and Y atoms relative to the axis defined by the CH3 fragment, coordinates based on stereographic projection are introduced. These coordinates yield a kinetic energy operator free of singularities within the dynamically relevant region. Employing this curvilinear coordinate system, full-dimensional and reduced dimensional MCTDH calculations study the cumulative reaction probability (for J = 0) and the thermal rate constant for the H+CH4 reaction on the Jordan-Gilbert potential energy surface [J. Chem. Phys. 102, 5669 (1995) ]. The full-dimensional results agree very well with previous full-dimensional MCTDH results which used transition state based normal coordinates. The results of our eight-dimensional (8D) calculations are in reasonable agreement with the full-dimensional ones. They deviate significantly from older 8D results of Zhang et al. [J. Chem. Phys. 127, 234213 (2007)] but agree well with more recent results from the same group.

© 2010 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. REACTION RATE CALCULATIONS
  3. COORDINATE SYSTEM
  4. KINETIC ENERGY OPERATOR
  5. SYSTEM DETAILS
  6. RESULTS AND DISCUSSION
    1. Full-dimensional calculation
    2. Reduced dimensional models
  7. CONCLUSIONS

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KEYWORDS and PACS

Keywords

atom-molecule reactions, hydrogen neutral atoms, organic compounds, reaction kinetics theory, reaction rate constants, SCF calculations

PACS

  • 82.30.Cf

    Atom and radical reactions; chain reactions; molecule-molecule reactions

  • 82.20.Xr

    Quantum effects in rate constants (tunneling, resonances, etc.)

  • 82.20.Pm

    Rate constants, reaction cross sections, and activation energies

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3304920

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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