Kinetics and product branching fractions of reactions between a cation and a radical: Ar(+) + CH3 and O2(+) + CH3.

Abstract

A novel technique is described for the measurement of rate constants and product branching fractions of thermal reactions between cation and radical species. The technique is a variant of the variable electron and neutral density attachment mass spectrometry (VENDAMS) method, employing a flowing afterglow-Langmuir probe apparatus. A radical species is produced in situ via dissociative electron attachment to a neutral precursor; this allows for a quantitative derivation of the radical concentration and, as a result, a quantitative determination of rate constants. The technique is applied to the reactions of Ar(+) and O2(+) with CH3 at 300 K. The Ar(+) + CH3 reaction proceeds near the collisional rate constant of 1.1 × 10(-9) cm(3) s(-1) and has three product channels: → CH3(+) + Ar (k = 5 ± 2 × 10(-10) cm(3) s(-1)), → CH2(+) + H + Ar (k = 7 ± 2 × 10(-10) cm(3) s(-1)), → CH(+) + H2 + Ar (k = 5 ± 3 × 10(-11) cm(3) s(-1)). The O2(+) + CH3 reaction is also efficient, with direct charge transfer yielding CH3(+) as the primary product channel. Several results needed to support these measurements are reported, including the kinetics of Ar(+) and O2(+) with CH3I, electron attachment to CH3I, and mutual neutralization of CH3(+) and CH2(+) with I(-).