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An efficient route to thermal rate constants in reduced dimensional quantum scattering simulations: Applications to the abstraction of hydrogen from alkanes

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10.1063/1.3625960

### Abstract

We present an efficient approach to the determination of two-dimensional potential energy surfaces for use in quantum reactive scattering simulations. Our method involves first determining the minimum energy path (MEP) for the reaction by means of an *ab initio* intrinsic reaction coordinate calculation. This one-dimensional potential is then corrected to take into account the zero point energies of the spectator modes. These are determined from Hessians in curvilinear coordinates after projecting out the modes to be explicitly treated in quantum scattering calculations. The final (1 + 1)-dimensional potential is constructed by harmonic expansion about each point along the MEP before transforming the whole surface to hyperspherical coordinates for use in the two-dimensional scattering simulations. This new method is applied to H-atom abstraction from methane, ethane and propane. For the latter, both reactive channels (producing *i*-C_{3}H_{7} or *n*-C_{3}H_{7}) are investigated. For all reactions, electronic structure calculations are performed using an efficient, explicitly correlated, coupled cluster methodology (CCSD(T)-F12). Calculated thermal rate constants are compared to experimental and previous theoretical results.

© 2011 American Institute of Physics

Received 07 April 2011
Accepted 28 July 2011
Published online 07 September 2011

Acknowledgments: It is a pleasure to thank Dr. Sarah M. Remmert and Dr. Ivan Ljubić for stimulating discussions. Support by the Engineering and Physical Sciences Research Council (Grant No. EP/G00224X/1) and the United States Office for Naval Research (Grant No. N00014-05-1-0460) is gratefully acknowledged. Parts of the calculations were done in a collaboration project with Professor Bernd Hartke, at the University Computing Center Kiel (Germany).

Article outline:

I. INTRODUCTION

II. THEORETICAL BACKGROUND

A. Reduced dimensional framework

B. Hyperspherical coordinates

C. Quantum scattering methodology

D. Kinetics

III. THE H + CH_{4}REACTION

A. Reaction pathway

B. Potential energy surface

C. Reaction probabilities

D. Thermal rate constants

IV. THE H + C_{2}H_{6}REACTION

A. Reaction pathway

B. Thermal rate constant

V. THE H + C_{3}H_{8}REACTION

A. Reaction pathway

B. Thermal rate constant

C. Number of *ab initio* points

VI. CONCLUSIONS

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2011-09-07

2014-04-19

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