Laser-induced fluorescence of the trans-CHBrCHO radical.

A new laser-induced fluorescence spectrum was observed in the region of 350 nm-360 nm. The spectrum was observed in the reaction between the CHBrCHBr and OH radicals and in the reaction of CHBrCHBr and CHCHBr with atomic oxygen O(P). The spectrum was assigned to the B̃--X̃ transition of the trans-CHBrCHO (trans-2-bromovinoxy) radical.

Rate Constants for Reactions of HCCO and HCCCO Radicals with O over the Temperature Range 243-423 K.

A pulsed laser photolysis-photoionization mass spectrometer system has been employed to measure the rate constants of HCCO + O and HCCCO + O over the temperature range 243-423 K in 1.2-8.4 Torr of He or N.

Laser-induced fluorescence of the CHFCHO radical and reaction of OH radicals with halogenated ethylenes.

A new laser-induced fluorescence spectrum of the 2-fluorovinoxy (CHFCHO) radical was first observed around 335 nm. The radical was produced in the reaction of an OH radical with 1,2-difluoroethylene (CHF=CHF). A single weak band was observed, which was assigned to the 0 band of the B̃-X̃ transition of the trans-CHFCHO radical.

Multireference configuration interaction calculation of the B(2)a"-X(2)a" transition of halogen- and methyl-substituted vinoxy radicals.

Ground and second excited electronic states of halogen and monomethyl substituted vinoxy radicals were studied by multireference configuration interaction (MRCI) calculation. Optimized geometries, rotational constants and vibrational frequencies of vinoxy and 1-fluorovinoxy showed good agreement with experimental values. Differences in calculated and observed B-X electronic transition energies were less than 0.