Mechanistic dichotomy in the gas‐phase addition of NO3 to polycyclic aromatic hydrocarbons: Theoretical study. Issue 16 (26th April 2018)

• Record Type: Journal Article
• Authors: Ghigo, Giovanni; Maranzana, Andrea; Tonachini, Glauco
• Is Part Of: International journal of quantum chemistry. Volume 118:Issue 16(2018)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2018-04-26
• Subjects: anthracene -- benzene -- B3LYP -- CASPT2 -- electron transfer -- naphthalene -- NO3 -- PAH -- pentacene -- state average; Quantum chemistry -- Periodicals; 541.28
• DOI: 10.1002/qua.25641
• Languages: English
• ISSNs: 0020-7608

Abstract

Abstract: The gas‐phase addition mechanism of the NO3 radical (an important tropospheric nocturnal oxidizing species) to some selected polycyclic aromatic hydrocarbons (PAHs), important pollutants of the troposphere, has been computationally analysed. Purpose of this work is to verify whether the reaction can take place through a mechanism different from the simple radical addition to the π aromatic system. This mechanism could consist in an Electron Transfer (ET) from the aromatics to NO3, thus generating an aromatic radical‐cation and a nitrate anion at long CO distances. The coulomb attraction should finally bind the two species and generate the radical adduct without any electronic energy barrier. The CASPT2 results show that, while benzene and naphthalene react with NO3 through a plain radical mechanism, anthracene reacts by a mechanism with a partial ET character, and pentacene reacts with a sort of inner‐sphere ET pathway. These results concur to explain the high reactivity of NO3 with larger PAHs whose ionization energy is below 7 eV and could be important in studies of environmental PAH oxidative degradation. Abstract : The gas‐phase reaction of radical NO3 proceeds with radical mechanism with Polycyclic Aromatic Hydrocarbons (PAHs) up to 3/4 fused rings, while with the PAHs with five or more fused benzene rings the reaction follows an inner‐phase Electron Transfer mechanism explain the high reactivity of NO3 with larger PAHs whose ionization energy is below 7 eV and could be important in studies of environmental PAH oxidative degradation.