Ring-Polymer Molecular Dynamics Rate Coefficient Calculations for Insertion Reactions: X + H2 → HX + H (X = N, O).
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.
†Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, United States.
Yongle
Y
Li
‡Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.|§Department of Mechanical and Aerospace Engineering, Combustion Energy Frontier Research Center, Princeton University, Olden Street, Princeton, New Jersey 08544, United States.
Yury V
YV
Suleimanov
†Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, United States.
Hua
H
Guo
insertion reaction; path integral; rate coefficients; tunneling; zero-point energy