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| - Argon Cluster-Mediated Trapping and Vibrational Spectroscopic Characterization of anOH-·HCH2• Intermediate in the O•- + CH4 Reaction
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| - We isolate an [O·CH4]•- intermediate in the reactive O•- + CH4 encounter using an argon cluster-mediatedtrapping technique and characterize it using vibrational predissociation spectroscopy. The spectra of the argon-solvated complexes establish that only the OH-·CH3• ion−radical adduct is prepared. Its formation is firmlyestablished by the appearance of the signature OH- stretching band close to that of the free hydroxide ion.The band origin locations and partially resolved rotational spacings indicate that hydroxide binds onto one ofthe methyl hydrogen atoms, much like the motif observed previously in the I-·HCH2• ion−radical complex.This OH-·CH3• species is best regarded as an entrance-channel complex in the secondary (endothermic)OH- + CH3• → H2O + CH2- proton transfer reaction. These observations indicate that the initial H-atomabstraction step (O•- + CH4 → OH- + CH3•) occurs too quickly to enable capture of the intermediatesdirectly associated with this process.
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