Temperature and Pressure Dependent Rate Coefficients for the Reaction of Ketene with Hydroxyl Radical.

The reaction of ketene with hydroxyl radical is drawing growing attention, for it is found to constitute an important step during the combustion of hydrocarbon and oxygenated hydrocarbon fuels, e.g., acetylene, propyne, allene, acetone, gasoline, diesel, jet fuels, and biofuels. We studied the potential energy surface (PES) of this reaction using B2PLYP-D3/cc-PVTZ for geometry optimization and composite methods based on CCSD(T)-F12/cc-PVTZ-F12 for energy calculations. From this PES, temperature- and pressure-dependent rate coefficients and branching ratios at 200-3000 K and 0.01-100 atm were derived using the RRKM/ME approach. The reaction is dominated by four product channels: (i) OH addition on the olefinic carbon of ketene to form CH