Lr. Brock et al., Laser-induced fluorescence spectroscopy of the (B)over-tilde(2)Pi-(X)over-tilde(2)A '' band system of HCCO and DCCO, J CHEM PHYS, 110(14), 1999, pp. 6773-6781
The electronic spectroscopy of the (B) over tilde( 2)II-(X) over tilde (2)A
" band system of the ketenyl radical, H(D)CCO, is investigated using laser
-induced fluorescence (LIF) in a free-jet environment. Vibronically resolve
d excitation spectra for HCCO are obtained from 33 400 cm(-1) to 35 100 cm(
-1); at higher energies the LIF spectra cutoff due to a rapid increase in t
he rate of predissociation. The parallel transitions from K-a" = 1 in the g
round state to the spin-orbit levels, (II3/2)-I-2 and (II1/2)-I-2, of the o
rigin of the (B) over tilde state are completely rotationally resolved for
both HCCO and DCCO. Four other parallel transitions originating from K-a" =
0 in the ground state and terminating on levels of Sigma vibronic symmetry
are observed and assigned to the two pairs of S states derived from one qu
antum of excitation in each of the Renner-Teller active modes, the CCO and
CCH(D) bend. Rotational analysis provides effective rotational constants an
d spin-rotation (orbit) couplings for each of these levels. In addition to
the Renner-Teller and spin-orbit couplings, there is substantial evidence f
or additional perturbations among the low-lying bending levels in the (B) o
ver tilde (II)-I-2 state of ketenyl. (C) 1999 American Institute of Physics
.