Kinetics for the Reactions of Ar+, O2+, and NO+ with Isoprene (2-Methyl-1,3-butadiene) as a Function of Temperature (300-500 K)

J Phys Chem A. 2023 Aug 31;127(34):7221-7227. doi: 10.1021/acs.jpca.3c03914. Epub 2023 Aug 16.

Abstract

Rate constants and product branching fractions were measured for reactions of Ar+, O2+, and NO+ with isoprene (2-methyl-1,3-butadiene C5H8) as a function of temperature. The rate constants are large (∼2 × 10-9 cm3 s-1) and increase with temperature, exceeding the ion-dipole/induced dipole capture rate. Adding a hard sphere term to the collision rate provides a more useful upper limit and predicts the positive temperature dependences. Previous kinetic energy-dependent rate constants show a similar trend. NO+ reacts only by non-dissociative charge transfer. The more energetic O2+ reaction has products formed through both non-dissociative and dissociative charge transfer, or possibly through an H atom transfer. The very energetic Ar+ has essentially only dissociative products; assumption of statistical behavior in the dissociation reasonably reproduces the product branching fractions.