ABSTRACT
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.
