Chemical generation of electronically excited ClF*(B3.pi.0+) and the B .fwdarw. X emission spectrum

Abstract

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", <veXe', ", " Ye') of the B and X states were calculated from the data. Twenty-one bands of the analogous transition in 37C1F were observed.

Chemiluminescent reactions of oxygen fluoride. 2. Reactions producing excited bromine fluoride and iodine fluoride

“…Measurement of the (3 0+) -*• "1") emission spectrum of electronically excited C1F was reported in a recent issue of this journal. 1 The excited GIF was produced by the reaction of chlorine atoms with gas phase 02F radicals in the presence of excited singlet molecular oxygen [02*(1 8,1 ?+)]. This first observation of emission from the GIF molecule suggests that mechanisms involving the 02F radical may also be used to generate the other halogen monofluorides BrF and IF in their excited (3 0+) states.…”

Chemiluminescent reactions of oxygen fluoride (O2F). 3. Reaction with magnesium atoms

“…The remainder of the apparatus was quite similar to that used in previous studies. 5 Emission spectra were recorded with a 0.3m McPherson monochromator, a cooled GaAs photomultiplier tube (RCA C31034), and a PAR photoncounting apparatus. Photon yields were measured by calibrating this system with techniques described previously.…”

“…Photon yields were measured by calibrating this system with techniques described previously. 5 The pressure in the system was measured with an MRS Baratron capacitance manometer, and the flow rates of diluent and carrier gases were monitored with Tylan mass flowmeters.…”