A new approach toward transition state spectroscopy

作者:Prozument Kirill; Shaver Rachel Glyn; Ciuba Monika A; Muenter John S; Park G Barratt; Stanton John F; Guo Hua; Wong Bryan M; Perry David S; Field Robert W*
来源:Faraday Discussions, 2013, 163: 33-57.
DOI:10.1039/c3fd20160k

摘要

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 S-0 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.

  • 出版日期2013