| Abstract
| - The QCISD and QCISD(T) quantum chemical methods have been used to characterize the energetics ofvarious possible mechanisms for the formation of HCF2+ from the bond-forming reaction of CF32+ with H2.The stationary points on four different pathways leading to the product combinations HCF2+ + H+ + F andHCF2+ + HF+ have been calculated. All four pathways begin with the formation of a collision complex[H2−CF3]2+, followed by an internal hydrogen atom migration to give HC(FH)F22+. In two of the mechanisms,immediate charge separation of HC(FH)F22+ via loss of either HF+ or a proton, followed by loss of an Fatom, yields the experimentally observed bond-forming product HCF2+. For the other two mechanisms, internalhydrogen rearrangement of HC(FH)F22+ to give C(FH)2F2+, followed by charge separation, yields the productCF2H+. This product can then overcome a 2.04 eV barrier to rearrange to the HCF2+ isomer, which is 1.80eV more stable. All four calculated mechanisms are in agreement with the isotope effects and collision energydependencies of the product ion cross sections that have been previously observed experimentally followingcollisions between CF32+ and H2/D2. We find that in this open-shell system, CCSD(T) and QCISD(T) T1-diagnostic values of up to 0.04 are acceptable. A series of angularly resolved crossed-beam scatteringexperiments on collisions of CF32+ with D2 have also been performed. These experiments show two distinctchannels leading to the formation of DCF2+. One channel appears to correspond to the pathway leading tothe ground state 1DCF2+ + D+ + F product asymptote and the other to the 3DCF2+ + D+ + F productasymptote, which is 5.76 eV higher in energy. The experimental kinetic energy releases for these channels,7.55 and 1.55 eV respectively, have been determined from the velocities of the DCF2+ product ion and arein agreement with the reaction mechanisms calculated quantum chemically. We suggest that both of theseobserved experimental channels are governed by the reaction mechanism we calculate in which chargeseparation occurs first by loss of a proton, without further hydrogen atom rearrangement, followed by loss ofan F atom to give the final products 1DCF2+ + D+ + F or 3DCF2+ + D+ + F.
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