First-Principles Reaction Dynamics beyond Six-Atom Systems

Abstract

Moving beyond the six-atomic benchmark systems, we discuss the new age and future of first-principles reaction dynamics, which investigates complex, multichannel chemical reactions. We describe the methodology starting from the benchmark ab initio characterization of the stationary points, followed by full-dimensional potential energy surface (PES) developments and reaction dynamics computations. We highlight our composite ab initio approach providing benchmark stationary-point properties with subchemical accuracy, the Robosurfer program system enabling automatic PES development, and applications for the Cl + C2H6, F + C2H6, and OH- + CH3I post-six-atom reactions focusing on ab initio issues and their solutions as well as showing the excellent agreement between theory and experiment.