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Volume 163, 2013
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A new approach toward transition state spectroscopy

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Chirped-Pulse millimetre-Wave (CPmmW) rotational spectroscopy provides a new class of information about photolysis transition state(s). Measured intensities in rotational spectra determine species-isomer-vibrational populations, provided that the rotational populations can be thermalized. The formation and detection of S0 vinylidene is discussed in the limits of low and high initial rotational excitation. CPmmW spectra of 193 nm photolysis of vinyl cyanide (acrylonitrile) contain J = 0–1 transitions in more than 20 vibrational levels of HCN and HNC, but no transitions in vinylidene or highly excited local-bender vibrational levels of acetylene. Reasons for the non-observation of the vinylidene co-product of HCN are discussed.

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Publication details

The article was received on 29 Dec 2012, accepted on 01 Feb 2013 and first published on 01 Feb 2013

Article type: Paper
DOI: 10.1039/C3FD20160K
Citation: Faraday Discuss., 2013,163, 33-57

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    A new approach toward transition state spectroscopy

    K. Prozument, R. G. Shaver, M. A. Ciuba, J. S. Muenter, G. B. Park, J. F. Stanton, H. Guo, B. M. Wong, D. S. Perry and R. W. Field, Faraday Discuss., 2013, 163, 33
    DOI: 10.1039/C3FD20160K

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