title: A new approach toward transition state spectroscopy.
abstract: 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.
authors.affiliation: MIT, Department of Chemistry, Cambridge, MA 02139, USA. kuyanov@mit.edu
authors.forename: Kirill
authors.initials: K
authors.lastname: Prozument
authors.forename: Rachel Glyn
authors.initials: RG
authors.lastname: Shaver
authors.forename: Monika A
authors.initials: MA
authors.lastname: Ciuba
authors.forename: John S
authors.initials: JS
authors.lastname: Muenter
authors.forename: G Barratt
authors.initials: GB
authors.lastname: Park
authors.forename: John F
authors.initials: JF
authors.lastname: Stanton
authors.forename: Hua
authors.initials: H
authors.lastname: Guo
authors.forename: Bryan M
authors.initials: BM
authors.lastname: Wong
authors.forename: David S
authors.initials: DS
authors.lastname: Perry
authors.forename: Robert W
authors.initials: RW
authors.lastname: Field