Benchmark ab initio characterization of the multi-channel Cl + CH3X [X = F, Cl, Br, I] reactive potential energy surfaces

Abstract

We determine benchmark geometries and relative energies for the stationary points of the Cl + CH₃X [X = F, Cl, Br, I] reactions. We consider four possible reaction pathways: hydrogen abstraction, hydrogen substitution, halogen abstraction, and halogen substitution, where the substitution processes can proceed via either Walden inversion or front-side attack. We perform geometry optimizations and obtain harmonic vibrational frequencies at the explicitly-correlated UCCSD(T)-F12b/aug-cc-pVTZ level of theory, followed by UCCSD(T)-F12b/aug-cc-pVQZ single-point computations to make finite-basis-set error negligible. To reach chemical (<1 kcal mol⁻¹), or even subchemical (<0.5 kcal mol⁻¹) accuracy, we include core-correlation, scalar relativistic, post-(T), spin–orbit-splitting and zero-point-energy contributions, as well, in the relative energies of all the stationary points. Our benchmark 0 K reaction enthalpies are compared to available experimental results and show good agreement. The stationary-point structures and energetics are interpreted in terms of Hammond's postulate and used to make predictions related to the dynamical behavior of these reactive systems.