Nitroso Oxides: Their Properties and Role in Photochemistry

Abstract

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RRKM and Ab Initio Investigation of the NH (X) Oxidation by Dioxygen

“…In accordance with a number of previous investigations, 12,27,43,44 we demonstrated the coexistence of the cis and trans forms of hydrogen nitrosyl oxide with the preponderance of cis-HNOO, the cis/trans energy gap was found to be 8.1-10.9 kJ • mol -1 . Contrary to thermodynamics, formation of the trans form of HNOO is favorable as it follows from the PES curvature for both conformers (Figure 3).…”

“…A lot of calculations ultimately predict that the cis form is more stable. The cis / trans energy gap depends on the level of theory being 18.0 kJ·mol −1 (CASSCF(6;6)/6-31G(d,p)), 5.0 kJ·mol −1 (MP4(SDTQ)//MP2/6-31G(d,p)), 7.5 kJ·mol −1 (MP2/6-31G(d,p)), and 16.7 kJ·mol −1 (B3LYP/6-31G(d)). To our knowledge, the only quantum chemical study performed at the MRD-CI//MCSCF(6;6)/6-31G(d,p) level of theory testifies to the higher stability of the trans form by 3.0 kJ·mol −1 .…”

“…The chemistry of nitroso oxides is complicated by evidence of the participation of triplet electronic states in the reactions of ArNOO. [11][12][13][14] The lack of information on nitroso oxides is caused by the fact that these particles are difficult to access for both experimental and theoretical studies. Even the parent nitroso oxide HNOO is known to be the challenging object for theoretical modeling.…”

“…In particular, the question of formation of the nitroso compound, which is one of the major photo-oxidation products, is left open. The chemistry of nitroso oxides is complicated by evidence of the participation of triplet electronic states in the reactions of ArNOO. – …”