Prediction of (•)OH-Initiated and (•)NO(3)-Initiated Transformation Products of Polycyclic Aromatic Hydrocarbons by Electronic Structure Approaches

[Image: see text] The abiotic reaction products of polycyclic aromatic hydrocarbons (PAHs) with hydroxyl radicals ((•)OH) and nitrate radicals ((•)NO(3)) are nitro-, oxygen-, and hydroxyl-containing PAHs (NPAHs, OPAHs, and OHPAHs). Four methods of the highest occupied molecular orbital (HOMO), Fukui function (FF), dual descriptor (DD), and population of π electrons (PP-π) are selected to predict the chemical reactivity of PAHs attacked by (•)OH and (•)NO(3) in this study. The predicted (•)OH-initiated and (•)NO(3)-initiated transformation products are compared with the main PAH transformation products (PAH-TPs) observed in the laboratory. The results indicate that PP-π and DD approaches fail to predict the transformation products of fused PAHs containing five-membered rings. By predicting the PAH-TPs of 13–14 out of the 15 parent PAHs accurately, HOMO and FF methods were shown to be suitable for predicting the transformation products formed from the abiotic reactions of fused PAHs with (•)OH and (•)NO(3).