Reactions of Ethynyloxy Radical with Hydroperoxyl Radical: Bridging Theoretical Reaction Dynamics and Chemical Modeling of Combustion.

Abstract

A detailed and accurate combustion reaction mechanism is crucial for understanding the nature of fuel combustion. In this work, a theoretical study of reaction HCCO+HO2 using M06-2X/6-311++G(d,p) for geometry optimization and combined methods based on spin-unrestricted CCSD(T)/CBS level of theory with basis set extrapolation from MP2/aug-cc-pVnZ (n=T and Q) for energy calculations were performed. The temperature- and pressure-dependent rate coefficients at 300-2000 K and 0.01-100 atm, suitable for combustion conditions, were derived using the Rice-Ramsberger-Kassel-Marcus/Master-Equation approach. Furthermore, temperature-dependent thermochemistry data of key species for the HCCO+HO2 system has also been studied. Finally, an updated ketene model is developed by supplementing the most recent theoretical work and the theoretical work in this paper. This updated model was tested to simulate the speciation of ketene oxidation in available experimental research. It is shown that the updated model for predicting ketene oxidation exhibits a high level of agreement with experimental data across a wide range of species profiles. An analysis was conducted to identify the crucial reactions that influence ketene ignition. This paper's research findings are essential for enhancing the combustion mechanism of ketene and other hydrocarbons and oxygenated hydrocarbon fuels.