First-Principles Theory for the H + CH 4 → H 2 + CH 3 Reaction
- 24 December 2004
- journal article
- other
- Published by American Association for the Advancement of Science (AAAS) in Science
- Vol. 306 (5705), 2227-2229
- https://doi.org/10.1126/science.1104085
Abstract
A full-dimensional quantum dynamics simulation of a hydrogen atom reacting with methane on an accurate ab initio potential energy surface is reported. Based on first-principles theory, thermal rate constants are predicted with an accuracy comparable to (or even exceeding) experimental precision. The theoretical prediction is within the range of the significantly varied experimental rate constants reported by different groups. This level of accuracy has previously been achieved only for smaller, three-or four-atom reactive systems. Comparison with classical transition state theory confirms the importance of quantum mechanical tunneling for the rate constant below 400 kelvin.Keywords
This publication has 36 references indexed in Scilit:
- Ab initio rate constants from hyperspherical quantum scattering: Application to H+CH4→H2+CH3The Journal of Chemical Physics, 2004
- A seven-dimensional quantum study of the H+CH4 reactionThe Journal of Chemical Physics, 2002
- Rate Constants for the CH4 + H → CH3 + H2 Reaction Calculated with a Generalized Reduced-Dimensionality MethodThe Journal of Physical Chemistry A, 2002
- A reduced dimensionality, six-degree-of-freedom, quantum calculation of the H+CH4→H2+CH3 reactionThe Journal of Chemical Physics, 2001
- The importance of an accurate CH4 vibrational partition function in full dimensionality calculations of the H+CH4→H2+CH3 reactionThe Journal of Chemical Physics, 2001
- Full dimensional quantum calculations of the CH4+H→CH3+H2 reaction rateThe Journal of Chemical Physics, 2000
- Application of semirigid vibrating rotor target model to reaction of H+CH4→CH3+H2The Journal of Chemical Physics, 2000
- Four-dimensional quantum scattering calculations on the H+CH4→H2+CH3 reactionThe Journal of Chemical Physics, 1999
- Polyatomic molecular potential energy surfaces by interpolation in local internal coordinatesThe Journal of Chemical Physics, 1998
- Classical trajectory studies of the reaction CH4+H→CH3+H2The Journal of Chemical Physics, 1995