Quasiclassical trajectory calculations of the HO2 + NO reaction on a global potential energy surface

Literature Information

Publication Date 2009-04-21
DOI 10.1039/B823031E
Impact Factor 3.676
Authors

Chao Chen, Benjamin C. Shepler, Bastiaan J. Braams, Joel M. Bowman


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Abstract

We report quasiclassical trajectory calculations of the HO2 + NO reaction using a new full dimensional, singlet potential energy surface (PES) which is a fit to more than 67 000 energies obtained with density functional theory-B3LYP/6-311G(d,p)-calculations. The PES is invariant with respect to permutation of like nuclei and describes all isomers of HOONO, HONO2, saddle points connecting them and the OH + NO2, HO2 + NO channels. Quasiclassical trajectory calculations of cross-sections for the HO2 + NO to form HOONO, HONO2 and OH + NO2 are done using this PES, for reactants in the ground vibrational state and rotational states sampled from a 300 K Boltzmann distribution. Trajectory calculations illustrate the pathway that HO2 + NO takes to the energized HOONO complex, which dissociates to products OH + NO2, reactants HO2 + NO, or isomerizes to HONO2. The association cross sections are used to obtain rate constants for formation of HOONO and HONO2 in the high-pressure limit, and formation of products OH + NO2 in the low-pressure limit.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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