UC Davis

Rate constants for the reactions of C⁺ + Cl^-, Br^-, and I^- were measured at 300 K using the variable electron and neutral density electron attachment mass spectrometry technique in a flowing afterglow Langmuir probe apparatus. Upper bounds of <10^-8 cm³ s^-1 were found for the reaction of C⁺ with Br^- and I^-, and a rate constant of 4.2 ± 1.1 × 10^-9 cm³ s^-1 was measured for the reaction with Cl^-. The C⁺ + Cl^- mutual neutralization reaction was studied theoretically from first principles, and a rate constant of 3.9 × 10^-10 cm³ s^-1, an order of magnitude smaller than experiment, was obtained with spin-orbit interactions included using a semiempirical model. The discrepancy between the measured and calculated rate constants could be explained by the fact that in the experiment, the total loss of C⁺ ions was measured, while the theoretical treatment did not include the associative ionization channel. The charge transfer was found to take place at small internuclear distances, and the spin-orbit interaction was found to have a minor effect on the rate constant.