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Issue 36, 2014
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Atmospheric formation of the NO3 radical from gas-phase reaction of HNO3 acid with the NH2 radical: proton-coupled electron-transfer versus hydrogen atom transfer mechanisms

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Abstract

The gas-phase reaction of nitric acid with the amidogen radical under atmospheric conditions has been investigated using quantum mechanical (QCISD and CCSD(T)) and DFT (B3LYP, BH&HLYP, M05, M05-2X, and M06-2X) calculations with the 6-311+G(2df,2p), aug-cc-pVTZ, aug-cc-pVQZ and extrapolation to the CBS basis sets. The reaction begins with the barrierless formation of a hydrogen-bonded complex, which can undergo two different reaction pathways, in addition to the decomposition back to the reactants. The lowest energy barrier pathway involves a proton-coupled electron-transfer mechanism, whereas the highest energy barrier pathway takes place through a hydrogen atom transfer mechanism. The performance of the different DFT functionals in predicting both the geometries and relative energies of the stationary points investigated has been analyzed.

Graphical abstract: Atmospheric formation of the NO3 radical from gas-phase reaction of HNO3 acid with the NH2 radical: proton-coupled electron-transfer versus hydrogen atom transfer mechanisms

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Supplementary files

Article information


Submitted
25 Jun 2014
Accepted
31 Jul 2014
First published
04 Aug 2014

Phys. Chem. Chem. Phys., 2014,16, 19437-19445
Article type
Paper
Author version available

Atmospheric formation of the NO3 radical from gas-phase reaction of HNO3 acid with the NH2 radical: proton-coupled electron-transfer versus hydrogen atom transfer mechanisms

J. M. Anglada, S. Olivella and A. Solé, Phys. Chem. Chem. Phys., 2014, 16, 19437
DOI: 10.1039/C4CP02792B

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