Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 109, Issue 40, Pages 8989-8993Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp053661x
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Isotope effects in the reaction of hydroxyl radical with methane are investigated in a crossed-beam experiment. By exploiting different combinations of CH/OD + CH4/CD4/CHD3, a total of eight isotopically variant reactions are examined to decipher the dynamical consequence of both primary and secondary isotope effects. The most prominent observation is from isotopic substitution of the transferred atom (primary isotope effect), which yields more stretch-excited water product for the D atom case than H atom. The opposite is found, however, for excitations in bending and combination modes. The secondary isotope effects, from either substituted hydroxyl radical or the three H atoms that are not being abstracted, are relatively minor and manifest themselves in spreading the vibrational distribution of the water coproducts.
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