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

被引：18

作者：

Anglada, Josep M. ^{[1
]}

Olivella, Santiago ^{[1
]}

Sole, Albert ^{[2
,3
]}

机构：

[1] CSIC, IQAC, Dept Quim Biol & Modelitzacio Mol, E-08034 Barcelona, Catalonia, Spain

[2] Univ Barcelona, Fac Fis, E-08028 Barcelona, Catalonia, Spain

[3] Univ Barcelona, Inst Quim Teor & Computac IQTCUB, E-08028 Barcelona, Catalonia, Spain

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2014年 / 16卷 / 36期

关键词：

JANAF THERMOCHEMICAL TABLES; SELF-CONSISTENT-FIELD; AB-INITIO; NITRIC-ACID; SYMMETRY-BREAKING; VIBRATIONAL-SPECTRA; MOLECULAR CALCULATIONS; DENSITY FUNCTIONALS; HYDROXYL RADICALS; RATE-CONSTANT;

D O I：

10.1039/c4cp02792b

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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.

引用

页码：19437 / 19445

页数：9