Modelling the absorption properties of polycyclic aromatic hydrocarbons and derivatives over three European cities by TD-DFT calculations

摘要

While brown carbon is a strongly-light-absorbing type of organic aerosol that is capable of significant regional radiative forcing, it has been neglected from climate models, which results in differences between model predictions and measured data. This also results from uncertainty regarding the relationship between the chemical composition of brown carbon and its optical properties. Herein, here was utilized a time-dependent density functional theory (TD-DFT) approach to model the "real-world" absorption of thirty polycyclic aromatic hydrocarbons (PAHs) and twenty-five derivatives (ten nitro-PAHs and fifteen oxygenated-PAHs) present in the atmosphere over three Southern European cities (Porto, Florence and Athens). These data were corrected both for "real-world" experimental concentration of these molecules over these cities, and for their theoretical fluorescence yield. These results indicate that the absorption of the molecules more relevant for climate forcing are at similar to 330, similar to 360 and similar to 440 nm. Furthermore, the absorption is explained mainly by PAH and oxygenated-PAH molecules, while nitro-PAHs provide only negligible contributions. Porto should be the city to be most affected by radiative forcing induced by these molecules, while Florence and Athens appear to be similarly affected. Finally, these models also demonstrate that absorption at similar to 330 nm is explained by both PAH and oxygenated-PAH-molecules, while absorption at similar to 360 and similar to 440 nmis only attributed to oxygenated-PAHs. More specifically, from the fifty-five studied molecules, only coronene (a PAH), 1,8-naphthalic anhydride, 6-H-benzo[cd]pyrene-6-one and 7H-benz[de]anthracence-7-one (three oxygenated-PAHs) provide relevant contributions to radiative forcing. (c) 2019 Elsevier B.V. All rights reserved.