Ring-Polymer Molecular Dynamics Rate Coefficient Calculations for Insertion Reactions: X + H2 → HX + H (X = N, O).

Abstract

The thermal rate constants of two prototypical insertion-type reactions, namely, N/O + H2 → NH/OH + H, are investigated with ring polymer molecular dynamics (RPMD) on full-dimensional potential energy surfaces using recently developed RPMDrate code. It is shown that the unique ability of the RPMD approach among the existing theoretical methods to capture the quantum effects, e.g., tunneling and zero-point energy, as well as recrossing dynamics quantum mechanically with ring-polymer trajectories leads to excellent agreement with rigorous quantum dynamics calculations. The present result is encouraging for future applications of the RPMD method and the RPMDrate code to complex-forming chemical reactions involving polyatomic reactants.