Publication costs assisted by Rockwell International Electronically excited C1F*(B3t0+) has been produced by the reaction of chlorine atoms with gas phase 02F radicals in the presence of singlet molecular oxygen. The 02F radicals were generated by the thermal decomposition of solid 02+AsF6". The results suggest that C1F*(B3t0+) is formed by a two-step process involving reaction of chlorine atoms with 02F followed by energy transfer from 02*(1Ag, 12g+). Forty bands of the B(3ir0+) -* ( +) transition in 35C1F were observed, and molecular constants (Te\ /, coe",

Publication costs asslsted by Rockwell InternationalChemiluminescence from electronically excited BrF and IF has been observed from reactions of molecular halides (Br2, Iz, ICl, and HI) with OzF. Much more intense emission is produced by reactions of bromine or iodine atoms with OzF in the presence of excited singlet molecular oxygen. The emission spectra and photon yields of these reactions are consistent with a proposed mechanism in which the X + OzF reactions produce vibrationally excited ground state XFt molecules. These may cross to the A W , ) state (if sufficient energy is available) or be pumped to the B(3110+) state by collisions with excited singlet oxygen. In the reactions of molecular halides with OzF, halogen atoms may be produced via formation and decomposition of a triatomic complex.

The radical molecule 02F has been shown to be a useful reagent in the chemical production of a number of electronically excited species.1"3 In each of these experiments, 02F radicals were generated from the thermal decomposition of solid 02+AsF6". The presence of gaseous 02F downstream of the decomposing solid was inferred from the strong absorption by the radical of light in the vicinity of 210 nm.2 We have obtained additional support for this inference by measurement of the UV absorption spectrum of the gaseous decomposition products of the 02+AsF6" salt. Using these absorption techniques, we also

Bei der Reaktion von Brg, I2, ICl und HI mit O2F (erzeugt durch thermische Zers. von festem OäAsFg ) wird Chemilumineszenz der elektronisch angeregten Moleküle BrF und IF beobachtet.

A series of experiments have been performed in which zinc atoms carried in a flowing stream of helium are excited to the 4(3P1) state by optical pumping with a XeCl excimer laser. Addition of calcium atoms to the flow results in quenching of the excited zinc atoms. The cross section for this energy transfer process is σ?3×10−16 cm2, corresponding to Zn(4 3PJ) quenching in fewer than 10 collisons with calcium atoms. Subsequent to optical excitation of the zinc atoms, emission was observed from both the 4 1P1 and 5 3S1 excited states of calcium. Integration of the intensities of the calcium emissions indicated that excitation of the singlet and triplet manifolds in calcium occurs with comparable probability, suggesting that spin conservation is not a strong constraint in the energy transfer process. Summation of the intensities indicate that the E–E transfer process accounts for most of the quenching of the excited zinc atoms.