Benchmark ab initio stationary-point characterization of the complex potential energy surface of the multi-channel Cl + CH3NH2 reaction.

Abstract

We characterize the exothermic low/submerged-barrier hydrogen-abstraction (HCl + CH2NH2/CH3NH) as well as, for the first time, the endothermic high-barrier amino-substitution (CH3Cl + NH2), methyl-substitution (NH2Cl + CH3), and hydrogen-substitution (CH2ClNH2/CH3NHCl + H) pathways of the Cl + CH3NH2 reaction using an accurate composite ab initio approach. The computations reveal a CH3NH2Cl complex in the entrance channel, nine transition states corresponding to different abstractions, Walden-inversion substitution, and configuration-retaining front-side attack substitution pathways, as well as nine post-reaction complexes. The global minima of the electronic and vibrationally adiabatic potential energy surfaces correspond to the pre-reaction CH3NH2Cl and post-reaction CH2NH2HCl complexes, respectively. The benchmark composite energies of the stationary points are obtained by considering basis-set effects up to the correlation-consistent polarized valence quadruple-zeta basis augmented with diffuse functions (aug-cc-pVQZ) using the explicitly-correlated coupled-cluster singles, doubles, and perturbative triples CCSD(T)-F12b method, post-(T) correlation up to CCSDT(Q) including full triples and perturbative quadruples, core correlation, and scalar relativistic and spin-orbit effects, as well as harmonic zero-point energy corrections.