First-Principles Theory for the H + CH4 → H2 + CH3 Reaction

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Science  24 Dec 2004:
Vol. 306, Issue 5705, pp. 2227-2229
DOI: 10.1126/science.1104085

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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.

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