Theoretical Study on the Kinetics of Secondary Oxygen Addition Reactions for N-Butyl Radicals.

Abstract

Chemical kinetics for second oxygen addition reactions (·QOOH + O₂) of long-chain alkanes are of great importance in low-temperature combustion technologies. However, kinetic data for key reactions of ·QOOH + O₂ systems are often difficult to obtain experimentally and are primarily estimated or calculated by using theoretical methods. In this work, barrier heights (BHs), reaction energies (ΔEs), and relative energies (REs) of stationary points for key reactions of two representative ·QOOH + O₂ systems in the low-temperature oxidation of n-butyl as well as pressure-dependent rate constants for the involved reactions are calculated with the high-level quantum chemical method CCSD(T)-F12b/CBS. These results can be employed in the development of low-temperature combustion mechanisms for n-butane and longer straight-chain alkanes. In addition, the performance of some quantum chemistry methods with a lower computational cost on BHs, ΔEs, and REs as well as rate constants is also investigated. Our results indicate that the maximum error on these energies with PNO-LCCSD(T)-F12a is within 1 kcal/mol, and rate constants with this method are in the best agreement with reference values, with a maximum relative error of about half the reference values. Due to its low computational cost and memory requirements, this method is strongly recommended for studying low-temperature combustion reactions involving larger hydrocarbon fuels.