MATRIX PHOTO-IONIZATION STUDIES OF TRIFLUOROMETHYL HALIDE SYSTEMS - INFRARED-SPECTRA OF CF3+, CF2X+, AND CF3X+ CATIONS IN SOLID ARGON

Photoionization of CF3X (X=CI, Br, I, and H) samples by argon resonance radiation during condensation with excess argon at 15 K produced new infrared absorptions which were separated into distinct groups by mercury arc photolysis. Bands slightly reduced by photolysis are assigned to the daughter cations CF3+ and CF2X+ which were photoneutralized by transfer of electrons from halide ions. Absorptions markedly decreased by 340-1000-nm photolysis with the concomitant growth of CF2X+ absorptions are assigned to parent cations CF3X+. Bands destroyed by 290-1000-nm photolysis are attributed to parent molecular anions. The cation CF3+ exhibits a very high v3 fundamental which is consistent with extensive η(p-p) bonding in this species. © 1978, American Chemical Society. All rights reserved.