The hydrogen abstraction reactions: a multireference Møller–Plesset perturbation (MRMP) theory study

Abstract

The hydrogen abstraction reactions, namely the reactions of H 2 with OH, trans-N 2H 2 with H, CH 4 with OH, and C 2H 6 with OH, are studied by multireference Møller–Plesset perturbation theory (MRMP) with a complete active space self-consistent field (CASSCF) reference function. We also examine the performance of density functional theory (DFT) with pure and hybrid functionals. In each case the exoergicity, barrier height, and transition state geometry are calculated. DFT methods fail to produce a correct barrier height for these radical reactions. MRMP gives values for the barrier height and exoergicity that are in reasonable agreement with experiment or an accurate estimate, supporting our use of this method as our `standard'.