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

Abstract

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.