Dynamics and kinetics of the OH + HO2 → H2O + O2 (1Δg) reaction on a global full-dimensional singlet-state potential energy surface

Literature Information

Publication Date 2020-10-28
DOI 10.1039/D0CP04611F
Impact Factor 3.676
Authors

Xiaoxiao Lu, Bina Fu, Dong H. Zhang


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Abstract

The OH + HO2 → H2O + O2 reaction is a prototype of radical–radical reactions, which plays an eminent role in combustion and atmosphere chemistry. Extensive studies have been focused on the ground triplet electronic state, but investigation on the singlet excited state is rare. Here, we report a full-dimensional singlet-state potential energy surface (PES) for this reaction, which was constructed using the fundamental invariant neural network (FI-NN) fitting to roughly 130 000 energy points calculated by the CASPT2/AVTZ method. Extensive quasiclassical trajectory (QCT) calculations were performed on the FI-NN PES in a wide range of collision energies and temperatures. The pathway via a shallow minimum with a direct abstraction mechanism is identified as a dominant reaction path due to a low barrier, with most available energy released into the rovibrational motion of the products, and angular distributions showing predominantly backward and sideways scattering amplitudes. The QCT thermal rate coefficients on the singlet-state PES show small, but non-negligible contributions to the overall rate of the OH + HO2 reaction.

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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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