Quantum electronic control on chemical activation of methane by collision with spin-orbit state selected vanadium cation.

By coupling a newly developed quantum-electronic-state-selected supersonically cooled vanadium cation (V+) beam source with a double quadrupole-double octopole (DQDO) ion-molecule reaction apparatus, we have investigated detailed absolute integral cross sections (σ's) for the reactions, V+[a5DJ (J = 0, 2), a5FJ (J = 1, 2), and a3FJ (J = 2, 3)] + CH4, covering the center-of-mass collision energy range of Ecm = 0.1-10.0 eV. Three product channels, VH+ + CH3, VCH2+ + H2, and VCH3+ + H, are unambiguously identified based on Ecm-threshold measurements. No J-dependences for the σ curves (σ versus Ecm plots) of individual electronic states are discernible, which may indicate that the spin-orbit coupling is weak and has little effect on chemical reactivity. For all three product channels, the maximum σ values for the triplet a3FJ state [σ(a3FJ)] are found to be more than ten times larger than those for the quintet σ(a5DJ) and σ(a5FJ) states, showing that a reaction mechanism favoring the conservation of total electron spin. Without performing a detailed theoretical study, we have tentatively interpreted that a weak quintet-to-triplet spin crossing is operative for the activation reaction. The σ(a5D0, a5F1, and a3F2) measurements for the VH+, VCH2+, and VCH3+ product ion channels along with accounting of the kinetic energy distribution due to the thermal broadening effect for CH4 have allowed the determination of the 0 K bond dissociation energies: D0(V+-H) = 2.02 (0.05) eV, D0(V+-CH2) = 3.40 (0.07) eV, and D0(V+-CH3) = 2.07 (0.09) eV. Detailed branching ratios of product ion channels for the titled reaction have also been reported. Excellent simulations of the σ curves obtained previously for V+ generated by surface ionization at 1800-2200 K can be achieved by the linear combination of the σ(a5DJ, a5FJ, and a3FJ) curves weighted by the corresponding Boltzmann populations of the electronic states. In addition to serving as a strong validation of the thermal equilibrium assumption for the populations of the V+ electronic states in the hot filament ionization source, the agreement between these results also confirmed that the V+(a5DJ, a5FJ, and a3FJ) states prepared in this experiment are in single spin-orbit states with 100% purity.