A novel technique for measurement of thermal rate constants and temperature dependences of dissociative recombination: CO2+, CF3+, N2O+, C7H8+, C7H7+, C6H6+, C6H5+, C5H6+, C4H4+, and C3H3+

A novel technique using a flowing afterglow-Langmuir probe apparatus for measurement of temperature dependences of rate constants for dissociative recombination (DR) is presented. Low (∼1011 cm−3) concentrations of a neutral precursor are added to a noble gas/electron afterglow plasma thermalized at 300–500 K. Charge exchange yields one or many cation species, each of which may undergo DR. Relative ion concentrations are monitored at a fixed reaction time while the initial plasma density is varied between 109 and 1010 cm−3. Modeling of the decrease in concentration of each cation relative to the non-recombining noble gas cation yields the rate constant for DR. The technique is applied to several species (O2+, CO2+, CF3+, N2O+) with previously determined 300 K values, showing excellent agreement. The measurements of those species are extended to 500 K, with good agreement to literature values where they exist. Measurements are also made for a range of CnHm+ (C7H7+, C7H8+, C5H6+, C4H4+, C6H5+, C3H3+, and C6H6+) derived from benzene and toluene neutral precursors. CnHm+ DR rate constants vary from 8–12 × 10−7 cm3 s−1 at 300 K with temperature dependences of approximately T−0.7. Where prior measurements exist these results are in agreement, with the exception of C3H3+ where the present results disagree with a previously reported flat temperature dependence.