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Volume 157, 2012
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Vibrationally resolved transition state spectroscopy of the F + H2 and F + CH4 reactions

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Abstract

The transition state regions of the F + para-H2, F + normal-H2, F + CH4 and F + CD4 reactions have been studied by slow electron velocity-map imaging (SEVI) spectroscopy of the anionic precursor clusters para-FH2, normal-FH2, FCH4 and FCD4. The F + H2 results improve on previously published photoelectron spectra, resolving a narrow peak that appears in the same position in the para-FH2 and normal-FH2 spectra, and suggesting that additional theoretical treatment is necessary to fully describe and assign the experimental results. A small peak in the para-FH2 results is also identified, matching simulations of a product resonance in the ν′ = 3 vibrational level. SEVI spectra of the 2P3/2 bands of FCH4 and FCD4 show extended structure from transitions to the entrance valley van der Waals region and the reactant side of the F + CH4 transition state region. Much of this structure is attributed to bending or hindered rotation of the methane moiety and may be a spectroscopic signature of reactive resonances.

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Publication details

The article was received on 28 Jan 2012, accepted on 15 Feb 2012 and first published on 23 Jul 2012


Article type: Paper
DOI: 10.1039/C2FD20011B
Citation: Faraday Discuss., 2012,157, 399-414
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    Vibrationally resolved transition state spectroscopy of the F + H2 and F + CH4 reactions

    T. I. Yacovitch, E. Garand, J. B. Kim, C. Hock, T. Theis and D. M. Neumark, Faraday Discuss., 2012, 157, 399
    DOI: 10.1039/C2FD20011B

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