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

Journal Article · · Journal of Physical Chemistry Letters
DOI:https://doi.org/10.1021/jz500062q· OSTI ID:1369849
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. Lastly, the present result is encouraging for future applications of the RPMD method and the RPMDrate code to complex-forming chemical reactions involving polyatomic reactants.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Combustion Energy Frontier Research Center (CEFRC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
DOE Contract Number:
SC0001198
OSTI ID:
1369849
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 4 Vol. 5; ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English