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Journal of Structural Chemistry

2011 year, number 3

A STUDY OF THE STRUCTURE OF high-energy STATES OF NITROGEN TRIOXIDE AND the (NO)2 dimer: DFT calculationS WITHIN the symmetrized Kohn-SHAM formalism

I. I. Zakharov
Keywords: quantum chemical calculations, density functional theory (DFT), high-energy states, NO3 and (NO)2, molecular structure and reactivity, activation of N2 and N2O
Pages: 461-469


The electronic structure, geometry, and thermodynamic parameters of the high-energy states of NO3 and the (NO)2 dimer are calculated at the DFT B3LYP/6-311++G(3df) level within the symmetrized Kohn-Sham formalism. The results of the DFT calculation of the excited states of NO3 well agree with the experimental data and precise ab initio calculations. The reactivity of high-energy nitrogen trioxide in the activation of molecular nitrogen and nitrogen protoxide is analyzed. The assumption is substantiated that the Karavaev effect (gain of nitrogen oxides in an air mixture with nitric acid vapors) is due to the photochemical activation of molecular nitrogen in the presence of an NO3 high-energy state as a decomposition product of nitric acid.