Chemical Activation of a Deuterium Molecule by Collision with a Quantum Electronic State-Selected Vanadium Cation.

Abstract

By combining a newly developed spin-orbit electronic state-selected ion source for vanadium cations (V+) with a double quadrupole-double octopole mass spectrometer, we have investigated in detail the chemical reactivity or integral cross sections (σ's) for the reactions of V+[a5DJ (J = 0, 1), a5FJ (J = 1, 2), and a3FJ (J = 2, 3)] ion with a deuterium molecule (D2). The vanadium deuteride ion (VD+) is identified to be the only product ion formed in the center-of-mass collision energies of Ecm = 0.1-10.0 V. No J dependence for the σ's is discernible for individual electronic states, indicating that the spin-orbit coupling is weak and has little effect on the chemical reactivity of the titled reaction. The maximum σ value for the V+(a3FJ) state [σ(a3FJ)] is about 7 and 70 times larger than those for σ(a5DJ) and σ(a5FJ), respectively, showing that the triplet V+(a3FJ) state is dominantly more reactive than the quintet states. Although the V+(a5FJ) state is 0.3 eV higher than the V+(a5DJ) ground state, the chemical reactivity of the V+(a5FJ) state is significantly lower than that of the V+(a5DJ) state, clearly indicating that the differences in chemical activity observed are due to quantum electronic states rather than energy effects. The Ecm thresholds determined for σ(a5DJ), σ(a5FJ), and σ(a3FJ) are consistent with the respective energetics for the formation of VD+ from the V+(a5DJ, a5FJ, and a3FJ) + D2 reactions. The analysis of Ecm threshold measurements yields a bond energy of D0(V+-D) = 2.5 ± 0.2 eV, suggesting that the previously reported values are too low by up to 0.4 eV. The large differences for σ(a5DJ, a5FJ, and a3FJ) observed here indicate that the activation of D2 by a V+ ion can be efficiently controlled by selecting the V+ electronic state as well as the Ecm. The quantum state-selected σ values presented here can also serve as experimental benchmarks for first-principles theoretical reaction dynamics calculations.