Rotational Analyses of the Laser Induced Fluorescence Excitation Spectra of Jet-Cooled CF3O and CF3S

Fluorocarbon oxy and peroxy radicals

“…From the analyses of laserinduced fluorescence excitation spectra of jet-cooled CF 3 O radicals, the origin of the A 2 A 1 X 2 E transition was found to begin at 28552 cm À1 and three fundamentals in the electronic excited state n 3 ¼ 635, n 5 ¼ 626, and n 6 ¼ 426 cm À1 have been detected [68]. From the rotational fine structure of the transitions it was concluded that CF 3 O maintains C 3v symmetry in both the ground and excited state [67,68]. Five fundamentals, Jahn-Teller and spin-orbit coupling constants of high accuracy in the ground state have been determined from dispersed fluorescence spectroscopy on jet-cooled CF 3 O radicals [71].…”

“…Five fundamentals, Jahn-Teller and spin-orbit coupling constants of high accuracy in the ground state have been determined from dispersed fluorescence spectroscopy on jet-cooled CF 3 O radicals [71]. In all the above experimental studies the CF 3 O radicals were usually generated either by excimer laser photolysis (l ¼ 193 nm) of CF 3 OF or CF 3 OOCF 3 [67,68,70], or by thermal dissociation and IR multiphoton excitation with a CO 2 laser of CF 3 OOCF 3 [69]. Recently a complete spectroscopic characterisation of CF 3 O radicals [72] has been possible by using the very efficient precursors CF 3 OC(O)OOC(O)OCF 3 [73] and CF 3 OC(O)OOCF 3 [74].…”

“…Subsequently several laser-induced fluorescence [67][68][69][70] and dispersed fluorescence [69][70][71] spectra of CF 3 O radicals were recorded in the gas phase. From the analyses of laserinduced fluorescence excitation spectra of jet-cooled CF 3 O radicals, the origin of the A 2 A 1 X 2 E transition was found to begin at 28552 cm À1 and three fundamentals in the electronic excited state n 3 ¼ 635, n 5 ¼ 626, and n 6 ¼ 426 cm À1 have been detected [68]. From the rotational fine structure of the transitions it was concluded that CF 3 O maintains C 3v symmetry in both the ground and excited state [67,68].…”