Journal of Chemical Physics, Vol.100, No.10, 7348-7359, 1994
Guided-Ion Beam Measurements of X(+)+no (X=ar, N-2) Reactions
Cross section and product ion time-of-flight measurements are presented for the X(+)+NO (X=Ar, N-2) collision systems over a collision energy range of 0.1-20 eV (c.m.). The experiments are carried out in an octopole guided-ion beam apparatus. Charge transfer is the main channel observed and dissociative charge-transfer products are observed for collision energies equal to or greater than their respective thermodynamic thresholds. A weak channel leading to ArN+ and/or ArO+ is observed in the X=Ar system. The charge-transfer cross sections of the two collision systems are similar in magnitude and have approximately an E(-1/2) dependence at near-thermal collision energies. The near-thermal cross sections are significantly less than the Langevin-Gioumousis-Stevens predictions for a reaction mediated by ion-induced dipole interactions and complex formation. The time-of-flight distributions of the Ar+, N-2(+)+NO charge-transfer products are characteristic of near-resonant charge-transfer processes. At all collision energies studied, the charge-transfer reaction is dominated by a direct mechanism, but below 1 eV, the formation of a long-lived intermediate complex is also significant. The results are discussed in relation to statistical models and to constraints imposed by requirements of energy resonance and Franck-Condon overlap in charge-transfer reaction dynamics.