Atmospheric oxidation mechanism of naphthalene initiated by OH radical. A theoretical study

文献信息

发布日期 2011-12-07
DOI 10.1039/C2CP23271E
影响因子 3.676
作者

Zhijie Zhang, Ling Lin, Liming Wang


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摘要

The atmospheric oxidation mechanism of naphthalene (Nap) initiated by the OH radical is investigated using density functional theory at B3LYP and BB1K levels. The initial step is dominated by OH addition to the C1-position of Nap, forming radical C10H8-1-OH (R1), followed by the O2 additions to the C2 position to form peroxy radical R1-2OO, or by the hydrogen abstraction by O2 to form 1-naphthol. In the atmosphere, R1-2OO will react with NO to form R1-2O, undergo intramolecular hydrogen transfer from –OH to –OO to form R1-P2O1 radicals, or possibly undergo ring-closure to R1-29OO bi-cyclic radical; while the formation of other bi-cyclic intermediate radicals is negligible because of the extremely high Gibbs energy barriers of >100 kJ mol−1 (relative to R1+O2). The mechanism is different from the oxidation mechanism of benzene, where the bi-cyclic intermediates play an important role. Radicals R1-P2O1 will dissociate to 2-formylcinnamaldehyde, while R1-2O will be transformed to stable products C10H6O3via epoxide-like intermediates. A few reaction pathways suggested in previous experimental studies are found to be invalid.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 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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