Photoionization of gas‐phase bromotrifluoromethane and its complexes with methanol: State dependence of intracluster reactions

Weakly bound complexes of CF3Br molecules or of CF3Br and CH3OH were prepared in supersonic jet expansions and studied by photoionization mass spectrometry. Argon was present in the jet expansion to promote cooling of the complexes. Measured ionization potentials are CF3Br, 11.404±0.014 eV; (CF3Br)2, 11.10±0.02 eV; (CF3Br⋅CH3OH), 10.76±0.05 eV. The appearance potential of CF+3 from CF3Br was found to be 11.56±0.02 eV, and evidence is presented that this value is adiabatic. From this appearance potential, ΔH0f0(CF+3)=86.6±1.1 kcal mol−1. The magnitude of the spin–orbit splitting in X 2E CF3Br+ into E1/2 and E3/2 states dominates any Jahn–Teller distortion. The effects of these phenomena on the stability of X 2E CF3Br+ are discussed. The following dissociation channels were observed: CF+3 from X 2E CF3Br+, CF2Br+ from A 2A1 CF3Br+, Br+ from B 2A2 CF3Br+, and CF+2 from D 2E CF3Br+. (CF3⋅CH3OH)+ is not produced from neutral dimers, but is created when a CF3Br moiety embedded in a trimer or larger cluste...