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Volume 118, 2001
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Dynamics of harpooning studied by transition state spectroscopy Part III. Li···FCH3

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Abstract

The Van der Waals complex Li···FCH3 has been formed in a crossed molecular beam apparatus. The transition state (TS) for the reaction Li*(2p 2P) + FCH3 → LiF + CH3 was accessed at various configurations by laser-excitation of the Li···FCH3 complex by tunable visible radiation, λ1. Photoinduced depletion of the complex by excitation to this TS was found to occur across a broad range of λ1 from 570 to 850 nm. This ‘action spectrum ’ consisted of two broad regions located to either side of the atomic transition line of Li (2p 2P←2s 2S). The first region, between 700 and 850 nm, was dominated by sharp maxima in the depletion intensity. A broad peak with weakly-resolved structure characterized the second region, between 570 and 680 nm. These findings were interpreted by means of high-level ab initio calculations of the potential-energy surfaces in the TS region. The peaks in the photodepletion spectrum were assigned to specific electronic transitions, their shapes and intensities being explained in terms of calculated transition-dipole moments and rovibrational wavefunctions.

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Publication details

The article was received on 11 Dec 2000 and first published on 11 Jun 2001


Article type: Paper
DOI: 10.1039/B009877I
Citation: Faraday Discuss., 2001,118, 191-207

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    Dynamics of harpooning studied by transition state spectroscopy Part III. Li···FCH3

    A. J. Hudson, F. Y. Naumkin, H. Oh, J. C. Polanyi and S. A. Raspopov, Faraday Discuss., 2001, 118, 191
    DOI: 10.1039/B009877I

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