A quantum chemical study of the structure of O=NO-ON=O peroxide and the reaction mechanism of no oxidation in the gas phase

Abstract

A DFT/B3LYP method using the 6-311++G(3df) basis set is employed to calculate the geometric, electronic, and thermodynamic parameters of O=NO-ON=O peroxide as an isomer of N 2 O 4 dinitrogen tetraoxide. Calculations of the configuration interaction in a system of three paramagnetic particles with open shells have shown for the first time that the formation of cis-cis peroxide in the oxidation reaction of nitrogen oxide 2NO ( 2 ∏) + O 2 ( 3 ∑ g ) → O=NO-ON=O ( 1 A) proceeds without an energy barrier in accordance with recently performed studies. The molecular orbital scheme of the barrierless activation of molecular oxygen and the driving force of the NO oxidation reaction are considered. A spontaneous character of the process is based on the idea of spin-catalysis when the reaction proceeds in the two-triplet state with total zero spin. The obtained results are in agreement with the experimental data on a spontaneous and irreversible process characterized by the observed negative activation energy.

A proline mimetic for enantioselective aldol reaction: a quantum chemical study of a catalytic reaction with a sterically hindered l‐prolinamide derivative

“…Even qualitative estimation of energies was found to be correct . As a drawback, several examples had been reported where B3LYP and other density functionals resulted to qualitatively incorrect mechanistic prediction of even textbook reactions . In the present study, we verified that B3LYP/6‐31G(d) remains a reliable theory level by BSSE evaluation and inclusion of correlation effects not covered by the hybrid GGA approach.…”

Quantum Chemical Study of the Initial Step of Ozone Addition to the Double Bond of Ethylene

“…Incomplete account for nondynamic electron correlation by the DFT functionals can even result in qualitatively incorrect topology of the PES. Indeed, search for stationary points using various DFT functionals and verification by the composite CCSD(T)//DFT approximation can be unreliable, as shown in ref (cf., ref ), where not only quantitative disagreement between DFT and CCSD(T) results was observed but also qualitatively different PES topology (reaction mechanism) was determined. In our opinion, the stationary point search and full geometry optimization with the CCSD(T) and CASSCF methods is more reliable verification method.…”

Mechanistic Insight into the Catalytic NO Oxidation by the MIL-100 MOF Platform: Toward the Prediction of More Efficient Catalysts

“…As a preliminary stage, the gas-phase NO oxidation without any catalysts was considered with the exploration of bimolecular (eq 1) and ter-molecular (eq ) reactions (Figure S2): …”