  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 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, 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.
