Barrier heights, reaction energies and bond dissociation energies for RH + HO2 reactions with coupled-cluster theory, density functional theory and diffusion quantum Monte Carlo methods

Abstract

Hydrogen abstraction reactions by the HO₂ radical from hydrocarbon molecules are an important class of reactions in the autoignition of hydrocarbon fuels. Performance of DLPNO-CC and DFT methods using three hybrids and four double hybrids as well as FN-DMC with the single-Slater–Jastrow trial wavefunction on barrier heights and reaction energies of RH + HO₂ reactions as well as bond dissociation energies of the involved X–H molecules is evaluated by comparison with the highly accurate CCSD(T)-F12b/CBS results in this study. Our results show that the DLPNO-CCSD(T)-F12 method can achieve highly accurate barrier heights, reaction energies and X–H bond energies for RH + HO₂ reactions at a relatively low computational cost, and it is applicable to the H-abstraction reactions of larger molecules. Among all DFAs, MN15 and the employed double hybrids can achieve accurate barrier heights and reaction energies with MADs of less than or around 2 kJ mol⁻¹, but their error on X–H bond energies is more pronounced. Only DSD-BLYP and DSD-PBEB95 can provide X–H bond energies with MADs less than 4 kJ mol⁻¹. Considering dispersion correction in DFT calculations does not improve these barrier heights and reaction energies. The error of FN-DMC on barrier heights and reaction energies is slightly larger than that of MN15 and those of double hybrids, but it can achieve results within chemical accuracy for these reactions and the X–H bond energies.