A pulsed beam of Co+(3F4) crosses a pulsed beam of C3H8 or C3D8 gas under single collision conditions at collision energies of 0.01 eV and 0.21 eV. After a variable time delay t(ext) = 1-8 micros a fast high voltage pulse extracts product ions into a field-free flight tube for mass analysis. Consistent with earlier work, we observe prompt CoC3H6+ +H2 elimination products in 3:1 excess over CoC2H4+ +CH4 products at 0.21 eV on a 2-10 micros time scale. Long-lived CoC3H8+ complexes fragment predominantly back to Co+ +C3H8 reactants and to H2 elimination products on a 6-24 micros time scale. Density functional theory (B3LYP) calculations provide energies, geometries, and harmonic vibrational frequencies at key stationary points for use in a statistical rate model of the reaction. By adjusting two key multicenter transition state (MCTS) energies downward by 4-7 kcal mol(-1), we obtain good agreement with our decay time results and with the cross section versus collision energy of Armentrout and co-workers from 0.1-1.0 eV. B3LYP theory succeeds in finding relative energies of the MCTSs leading to CH4 and H2 in the proper order to explain the different product branching ratio for Co+ (which favors H2 over CH4) compared with its nearest neighbors Fe+ and Ni+ (which favor CH4 over H2).

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The velocity map imaging technique is applied to mass-selected CoC3H6++CH4 and CoC4H8++H2 elimination products from the Co+(3F4)+isobutane reaction studied under crossed-beam conditions at 0.21 eV collision energy. For both reactions we obtain the joint scattering probability distribution P(E,Θ), where E and Θ are the product translational energy and scattering angle. The fraction of available energy deposited into product translation is 0.4 for H2, compared with 0.1 for CH4. For the CH4 product, the angular distribution is forward-backwards symmetric and sharply peaked at Θ=0 and 180°. P(E,Θ) is not separable into the product of an energy and an angular function; rather, the angular distribution peaks more sharply at higher translational energy. Evidently, incipient CoC3H6++CH4 products equilibrate in the Co+(C3H6)(CH4) exit-channel well, from which they decay statistically. The product translational energy distribution P(E) is consistent with orbiting-transition state phase-space theory with no exit-channel barrier. In addition, the energy-integrated angular distribution T(Θ) is consistent with the predictions of the early statistical complex decay model of Miller and Herschbach for fragmentation from a transition state that is a prolate top. In sharp contrast, P(E) for the CoC4H8++H2 products exhibits a substantial hot, nonstatistical tail towards high energy. Perhaps the H2 channel has a late potential energy barrier some 0.5 eV above products, but we view this explanation as highly unlikely. Instead, we suggest that the potential energy from an earlier multicenter transition state is funneled efficiently, and highly nonstatistically, into product translation. This surprising conclusion may apply to H2 products for the entire family of reactions of the late-3D series transition metal cations Fe+, Co+, and Ni+ with alkanes.

The velocity map imaging technique is applied to mass-selected CoC2H4 + + CH4 and CoC3H6 + + H2 elimination products from the Co+(3F4) + propane reaction studied under crossed-beam conditions at 0.19 eV collision energy. For both products, we obtain the joint scattering probability distribution P(E,ϑ), where E and ϑ are the product translational energy and scattering angle. Both angular distributions are forward-backward symmetric and only modestly anisotropic. Both product translational energy distributions P(E) are in fairly good agreement with earlier results of Bowers and co-workers, indicating that the earlier distributions were dominated by reaction of ground-state Co+. The fraction of the total available energy deposited into product translation is 0.13 for CH4 and 0.44 for H2. For CH4 products, P(E) is cold and would be readily fit by orbiting-transition-state phase-space theory (OTS−PST) without an exit-channel barrier. Evidently, incipient CoC2H4 + + CH4 products equilibrate in the Co+(C2H4)(CH4) exit-channel well, from which they decay statistically. In sharp contrast, for H2 products P(E) exhibits a substantial hot, nonstatistical tail toward high energy, extending to the limits of the available energy. Although it is imaginable that the H2 channel has a late potential energy barrier some 0.5 eV above products, we view this as highly unlikely. Instead, we suggest that the potential energy from an earlier multi-center transition state MCTSH 2 is funneled efficiently, and highly nonstatistically, into product translation, although MCTSH 2 is far from product-like. We believe that H2 escapes on the same time scale as intramolecular vibrational redistribution (IVR) due to its light mass, the early potential energy decoupling of the migrating H atom from the incipient alkene moiety, and the weak kinetic energy coupling across the massive Co+ ion. This surprising conclusion seemingly applies to H2 products for the entire family of reactions of the late-3d series transition metal cations Fe+, Co+, and Ni+ with alkanes.

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