Formation of a Resonance-Stabilized Radical Intermediate by Hydroxyl Radical Addition to Cyclopentadiene.

Abstract

The reaction of the OH radical with cyclopentadiene (C5H6) was investigated at room temperature using multiplexed photoionization mass spectrometry. OH radicals in their ground electronic state were generated in the gas phase by 248 nm photolysis of H2O2 or 351 nm photolysis of HONO. Analysis of photoion spectra and temporal profiles reveal that at room temperature and over the 4-8 Torr pressure range, the resonance-stabilized 5-hydroxycyclopent-2-en-1-yl (C5H6OH) is the main observed reaction product. Abstraction products (C5H5) were not detected. The C5H6OH potential energy surface calculated at the CCSD(T)/cc-pVTZ//M06-2X/6-311++G** level of theory suggests that the resonance-stabilized radical product is formed through barrierless addition of the OH radical onto cyclopentadiene's π system to form a van der Waals complex. This weakly bound adduct isomerizes through a submerged energy barrier to the resonance-stabilized addition adduct. Master Equation calculations, including two OH-addition entrance pathways, predict that 5-hydroxycyclopent-2-en-1-yl remains the sole addition product up to 500 K. The detection of an OH-containing resonance-stabilized radical at room temperature further highlights their importance in carbon- and oxygen-rich environments such as combustion, planetary atmospheres, and the interstellar medium.