Ion-molecule reaction dynamics: Velocity map imaging studies of N(+) and O(+) with CD3OD

We present a study of the charge transfer reactions of the atomic ions N(+)and O(+) with methanol in the collision energy range from ∼2 to 4 eV. Charge transfer is driven primarily by energy resonance, although the widths of the product kinetic energy distributions suggest that significant interchange between relative translation and product vibration occurs. Charge transfer with CD3OD is more exoergic for N(+), and the nascent parent ion products appear to be formed in excited B̃ and C̃ electronic states, and fragment to CD2OD(+) by internal conversion and vibrational relaxation to the ground electronic state. The internal excitation imparted to the parent ion is sufficient to result in loss of one or two D atoms from the carbon atom. The less exoergic charge transfer reaction of O(+) forms nascent parent ions in the excited à state, and internal conversion to the ground state only results in ejection of single D atom. Selected isotopomers of methanol were employed to identify reaction products, demonstrating that deuterium atom loss from nascent parent ions occurs by C-D bond cleavage. Comparison of the kinetic energy distributions for charge transfer to form CD3OD(+) and CD2OD(+) by D atom loss with the known dynamics for hydride abstraction from a carbon atom provides strong evidence that the D loss products are formed by dissociative charge transfer rather than hydride (deuteride) transfer. Isotopic labeling also demonstrates that chemical reaction in the N(+) + CD3OD system to form NO(+) + CD4 does not occur in the energy range of these experiments, contrary to earlier speculation in the literature.