Kinetic Investigations of the CH (X2Π) Radical Reaction with Cyclopentadiene.

ABSTRACT

The reaction of the ground state methylidyne radical (CH (X2Π)) with cyclopentadiene (C5H6) is studied in a quasi-static reaction cell at pressures ranging from 2.7 to 9.7 Torr and temperatures ranging from 298 to 450 K. The CH radical is generated in the reaction cell by pulsed-laser photolysis (PLP) of gaseous bromoform at 266 nm, and its concentration monitored using laser-induced fluorescence (LIF) with an excitation wavelength of 430.8 nm. The reaction rate coefficient is measured to be 2.70(±1.34) × 10-10 cm3 molecule-1 s-1 at room temperature and 5.3 Torr and found to be independent of pressure or temperature over the studied experimental ranges. DFT and CBS-QB3 methods are used to calculate the reaction potential energy surface (PES) and to provide insight into the entrance channel of the reaction. The combination of the experimentally determined rate constants and computed PES supports a fast, barrierless entrance channel that is characteristic of CH radical reactions and could potentially lead to the formation of benzene isomers.