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

作者：Zhang Zhijie; Lin Ling; Wang Liming^*

来源：Physical Chemistry Chemical Physics, 2012, 14(8): 2645-2650.

DOI：10.1039/c2cp23271e

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 C-1-position of Nap, forming radical C10H8-1-OH (R1), followed by the O-2 additions to the C-2 position to form peroxy radical R1-2OO, or by the hydrogen abstraction by O-2 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 4100 kJ mol(-1) (relative to R1 + O-2). 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 C10H6O3 via epoxide-like intermediates. A few reaction pathways suggested in previous experimental studies are found to be invalid.

• 出版日期2012
• 单位华南理工大学