期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 113, 期 16, 页码 4255-4264出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp810803k
关键词
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资金
- United States Office [N00014-05-1-0460]
- Engineering and Physical Sciences Research Council [EP/G00224X/1]
- Oxford University Press
- Ramsay Memorial Fellowship
- Engineering and Physical Sciences Research Council [EP/G00224X/1, EP/E009824/1] Funding Source: researchfish
- EPSRC [EP/E009824/1, EP/G00224X/1] Funding Source: UKRI
The symmetric title reaction CH3 + CH4 -> CH4 + CH3 is studied using quantum scattering theory. Quantum dynamics calculations are performed in hyperspherical coordinates with a two-dimensional effective potential energy surface consisting of an analytical 18-parameter double Morse function fit to ab initio data at the CCSD(T)/cc-pVTZ//MP2/cc-pVTZ level of theory. Spectator modes are treated adiabatically by inclusion of projected zero-point energy corrections in the effective potential. The close-coupled equations are solved via R-matrix propagation. Energy and J-shifted thermal rate constants are compared to experimental data and highlight the importance of quantum tunneling. Oscillating reactivity and metastable bound state resonances are observed in the cumulative and state-to-state reaction probabilities. State-to-state differential and initial state-selected integral cross sections are presented and discussed. Primary and secondary kinetic isotope effects for two symmetric deuterated variants of the title reaction are also presented.
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