OXIDATION MECHANISM OF THE BUTADIYNYL RADICAL, C4H: ANALOGUE OF C2H OR NOT?

Abstract

Reactions of the carbon-chain radicals are of great importance in the combustion and astrophysical processes. The kinetics of the butadiynyl radical, C 4 H , has received recent attention. While there has been sufficient knowledge concerning the oxidation of the ethynyl radical, C 2 H , oxidation of the higher even-numbered members C 2n H (n > 1) is hardly known. In this paper, to enrich the C 4 H -chemistry, we report the first study of the oxidation mechanism of C 4 H . At the CCSD(T)/aug-cc-pVTZ//B3LYP/6-311++G(d,p)+ZPVE level, the potential energy surface (PES) survey is presented covering various product channels P1( CO + HC 3 O ) (-152.7 kcal/mol), P2( C 3 H + CO 2) (-117.9), P3( HCO + C 3 O ) (-108.5), P4( HC 4 O +3 O ) (-45.2), and P5( OH + C 4 O ) (-33.2) accompanied by the master equation rate constant calculations. Despite the similarity in the PES, the kinetics of C 4 H +3 O 2 differs dramatically from that of the analogous C 2 H +3 O 2 reaction. For the C 4 H +3 O 2 reaction, the O -abstraction product P4( HC 4 O +3 O ) is almost the exclusive product, whereas the lowest C , O -exchange product P1( CO + HC 3 O ) and other products have little importance. By contrast, the C 2 H +3 O 2 reaction favors the C , O -exchange product HCO + CO . Being overall barrierless and mainly associated with the molecular → atomic oxygen conversion, the C 4 H +3 O 2 reaction should play an important role in the soot formation and interstellar chemistry where C 4 H is involved.