The isomerization and dissociation channels for o-, m-, and p-pyridyl radicals are characterized at adiabatic ground state by utilizing the B3LYP/cc-pVTZ level of theory and the CCSD(T)/cc-pVTZ calculations. With facilitation of RRKM rate constants, out of the web of ab initio paths composed of 3 pyridyls, 208 intermediates, and 65 dissociated products, the most probable paths at 248 nm, thus reaction mechanism, are determined. Subsequently the corresponding rate equations are solved that the evolutions of concentrations of intermediates, and products versus time are obtained. As a result, the final products and yields are identified. This study predicts that while o-pyridyl (o-C5H4N; ) and m-pyridyl (m-C5H4N; )would most likely produce HCCHCN (cyanovinyl radical) + HCCH (ethylene) and HCCCHCHCN (cyanovinylacetylene) + H, HCCCHCHCN + H and HCCHCCH (2-acetylenylethylenyl radical) + HCN (hydrogen cyanide), respectively. p-Pyridyl yields (p-C5H4N; ) HCCHCCH + HCN.

Theoretical study on photodissociation of o-, m-, and p-pyridyl radicals

248th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.