Theoretical characterization of halogenated methylperoxy nitrites CX Y3−OONO (X, Y = H, F, Cl)

Theoretical Study on the Mechanism of the Reaction of CF3S with NO2

“…For instance, the lowest energy minima in the present fluorinated system are the CF 3 SONO species and specifically the cis-perpendicular configuration, while in CH 3 S + NO 2 , the CH 3 SNO 2 association minimum is located below both CH 3 SONO conformers. It is interesting to mention at this point that the nitrate isomers are also the lowest energy structures in the related reactions CX 3 O + NO 2 , X = H, F, , being more stable than the corresponding peroxides CX 3 OONO cp and CX 3 OONO tp . Table summarizes the heat of formation values for CX 3 YNO 2 and CX 3 YONO, X = F, H; Y = S, O.…”

Effect of Halogenation on the Mechanism of the Atmospheric Reactions between Methylperoxy Radicals and NO. A computational Study

“… a The first line of results for each halogenated species are based on the atomization energies, , the second line on eq , and the third line on the isodesmic scheme of eq . b From refs and . c This is the most recent Δ H f 298 value from ref . …”

“…McGivern et al , have examined several energy features of the brominated systems, NO + CH 2 BrO 2 , CHBr 2 O 2 , and CBr 3 O 2 , as part of the investigation of the atmospheric oxidation pathways of brominated methanes. Also Lesar et al , have recently studied the structural and thermodynamic properties of a series of chlorinated and fluorinated methyl peroxynitrites and nitrates. The interesting feature emerging from these limited studies is the increased stabilization of the intermediate alkyl peroxynitrite relevant to the alkylperoxy radical + NO reactants upon halogenation.…”

“…Hence, the enhancement of the rate coefficient and the increased reactivity of the halogenated reactions must originate from the differentiation of the PES relative to the CH 3 O 2 + NO surface rather than be attributed to a weakening of the halogenated peroxy bond as initially assumed. In fact, Lesar et al, in the examination of the structural features of quite a number of halogenated methyl peroxynitrites, have shown that halogenation brings no change to the peroxy bond distance in the intermediate peroxynitrites and no weakening of the peroxy bond. Instead, the main structural changes observed were the significant reduction of the COO bond and the severe elongation of the OON bond, whereas the peroxide bond distance remains entirely unaffected by the introduction of halogen atoms in the methylic group.…”

Quantum chemical topology: The electronic structure of the alkaline nitrites MONO (M = Li, Na, K) studied by means of topological analysis of the electron localization function

“…An electronic structure of the nitrous acid (HONO) and nitrites is usually studied within the framework of the molecular orbital theory 9–14. Recently, a topological analysis of the Electron Localization Function 15, within a framework of the Quantum Chemical Topology (QCT), 16 has been used to study the chemical bonding in HONO 17.…”