AN EXAMINATION OF PATHWAYS FOR THE REACTION OF O(P-3) ATOMS WITH FCO(2A') RADICALS

The reaction mechanism for the reaction of O(3P) atoms with FCO(2A′) radicals has been studied by means of ab initio quantum chemical techniques using polarized basis sets and including the effects of electron correlation and zero-point corrections. The mechanism involves the initial addition of O(3P) to the FCO(2A′) radical to form FC(O)O radicals, subsequently followed by fluorine elimination to form CO2(1Σg+). These results are consistent with experimental observations of Ryan and Plumb. The previously measured rate constant for the O(3P) + FCO(2A′) reaction is also suggested to be due solely to the following reaction which accounts for the loss of FCO(2A′) radicals: O(3P) + FCO(2A′) → [FC(O)O]‡ → F(2P) + CO2(1Σg++). © 1990 American Chemical Society.