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  1. By combining a newly developed two-color laser pulsed field ionization-photoion (PFI-PI) source and a double-quadrupole–double-octopole (DQDO) mass spectrometer, we investigated the integral cross sections ( σ s) of the vanadium cation (V + ) toward the activation of CO 2 in the center-of-mass kinetic energy ( E cm ) range from 0.1 to 10.0 eV. Here, V + was prepared in single spin–orbit levels of its lowest electronic states, a 5 D J ( J = 0–4), a 5 F J ( J = 1–5), and a 3 F J ( J = 2–4), with well-defined kinetic energies. For both product channels VO + + CO and VCO + + O identified, V + (a 3 F 2,3 ) is found to be greatly more reactive than V + (a 5 D 0,2 ) and V + (a 5 F 1,2 ), suggesting that the V + + CO 2 reaction system mainly proceeds via a “weak quintet-to-triplet spin-crossing” mechanism favoring the conservation of total electron spins. In addition, no J -state dependence was observed. The distinctive structures of the quantum electronic state selected integral cross sections observed as a function of E cm and the electronic state of the V + ion indicate that the difference in the chemical reactivity of the title reaction originated from the quantum-state instead of energy effects. Furthermore, this work suggests that the selection of the quantum electronic states a 3 F J ( J = 2–4) of the transition metal V + ion can greatly enhance the efficiency of CO 2 activation. 
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  2. null (Ed.)
    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 + [a 5 D J ( J = 0, 2), a 5 F J ( J = 1, 2), and a 3 F J ( J = 2, 3)] + CH 4 , covering the center-of-mass collision energy range of E cm = 0.1–10.0 eV. Three product channels, VH + + CH 3 , VCH 2 + + H 2 , and VCH 3 + + H, are unambiguously identified based on E cm -threshold measurements. No J -dependences for the σ curves ( σ versus E cm 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 a 3 F J state [ σ (a 3 F J )] are found to be more than ten times larger than those for the quintet σ (a 5 D J ) and σ (a 5 F J ) 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 (a 5 D 0 , a 5 F 1 , and a 3 F 2) measurements for the VH + , VCH 2 + , and VCH 3 + product ion channels along with accounting of the kinetic energy distribution due to the thermal broadening effect for CH 4 have allowed the determination of the 0 K bond dissociation energies: D 0 (V + –H) = 2.02 (0.05) eV, D 0 (V + –CH 2 ) = 3.40 (0.07) eV, and D 0 (V + –CH 3 ) = 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 (a 5 D J , a 5 F J , and a 3 F J ) 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 + (a 5 D J , a 5 F J , and a 3 F J ) states prepared in this experiment are in single spin–orbit states with 100% purity. 
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  3. null (Ed.)