Kinetics of the benzyl + HO and benzoxyl + OH barrierless association reactions: fate of the benzyl hydroperoxide adduct under combustion and atmospheric conditions.

Radical-radical association reactions are challenging to address theoretically due to difficulties finding the bottleneck that variationally minimizes the reactive flux. For this purpose, the variable reaction coordinate (VRC) formulation of the variational transition state theory (VTST) represents an appropriate tool. In this work, we revisited the kinetics of two radical-radical association reactions of importance in combustion modelling and poly-aromatic hydrocarbon (PAH) chemistry by performing VRC calculations: benzyl + HO2 and benzoxyl + OH, both forming the adduct benzyl hydroperoxide.

Multi-fuel surrogate chemical kinetic mechanisms for real world applications.

The most important driving force for development of detailed chemical kinetic reaction mechanisms in combustion is the desire by researchers to simulate practical systems. This paper reviews the parallel evolution of kinetic reaction mechanisms and applications of those models to practical, real engines. Early, quite simple, kinetic models for small fuel molecules were extremely valuable in analyzing long-standing, poorly understood applied ignition and flame quenching problems, and later kinetic models have been applied to much more complex flame propagation, problems including autoignition in spark-ignition engines and issues related to octane numbers and knock in modern, high compression ratio and other engines.