Reaction mechanism, rate constants, and product yields for the oxidation of embedded five-member ring radicals with atomic oxygen

Abstract

Oxidation mechanism of an embedded five-member ring on a surface of a carbonaceous particle with atomic oxygen has been studied employing G3(MP2,CC)//B3LYP/6-311G* potential energy surface calculations for C15H9 + O reactions. Temperature- and pressure-dependent reaction rate constants have been evaluated using the RRKM – Master Equation approach. The mechanism involves barrierless oxygen atom addition to a carbon atom on a free edge of a five-member ring followed by migration of the H atom from the attacked C atom to an ortho position followed by the five-member ring opening and elimination of the CO group, with the five-member ring being fully destroyed. When the embedded ring has three common sides with surrounding six-member rings and one free-edge carbon atom, the only product is the 4-phenanthrenyl radical. When the embedded ring has two common sides with the six-member rings and two free-edge C atoms, two different decarbonylation products possessing a phenalene core can be formed depending on the direction of the 1,2-H shift.