Theoretical Study of the Mechanism and Kinetics of the Oxidation of Cyclopenta[a]Naphthalenyl Radical C₁₃H₉ with Molecular Oxygen

Abstract

Electronic structure/Rice−Ramsperger−Kassel−Marcus Master equation calculations were applied to unravel the oxidation mechanism and kinetics of the cyclopenta[a]naphthalenyl radical with molecular oxygen. The reaction has been shown to proceed through the addition of O 2 in the orthoposition in the five-membered ring of C 13 H 9 . At low temperatures, the reaction yields a collisionally stabilized C 13 H 9 O 2 complex, which rapidly decomposes back to the reactants. In the high-temperature regime, above 800, 900, 1125, and 1375 K at pressures of 0.03, 1, 10, and 100 atm, respectively, the reaction forms bimolecular products including 3H-/1Hcyclopenta[a]naphthalen-3-one + OH as the prevailing product together with 1-ethanol-substituted 2-naphthyl radical + CO and 3H-benzo[f ]chromen-3-one + H as minor ones, with the branching ratio of the OH elimination channel growing with temperature and the rate constants for the individual bimolecular channels being independent of pressure. The calculated rate constants and product branching for cyclopenta[a]naphthalenyl + O 2 closely agree with those reported earlier for the indenyl + O 2 reaction and are recommended for the combustion kinetic models for the oxidation reactions of five-membered rings on free edges of larger polycyclic aromatic hydrocarbon molecules. The results also confirm that the oxidation of a π radical located on a five-membered ring with molecular oxygen is very slow.

Density Functional Theory Study of the Oxygen Reduction Reaction Mechanism on Graphene Doped with Nitrogen and a Transition Metal

“…The simulation results were visualized using the GaussView 6 software. The modeling was carried out by the density functional theory (DFT) method using the B3LYP functional , and the 6-31G* basis set, similar to the previous studies. , The effect of the solvent (water) was taken into account in the model of self-consistent reaction field (SCRF). , …”

“…The modeling was carried out by the density functional theory (DFT) method using the B3LYP functional 27,28 and the 6-31G* basis set, similar to the previous studies. 29,30 The effect of the solvent (water) was taken into account in the model of self-consistent reaction field (SCRF). 31,32 To analyze the catalytic parameters of materials, the surface regions of carbon materials were modeled using a fragment of graphene (10 conjugated aromatic rings) and fragments of graphene with nitrogen atoms and the studied metal incorporated in the structure, namely, a metal atom surrounded by four N atoms inside 10 conjugated aromatic rings (Figure 1).…”

Quantum-Chemical Modeling of the Catalytic Activity of Graphene Doped with Metal Phthalocyanines in ORR

“…The initial model structures and input files were created with the GaussView 6 program, and visualization was performed with the ChemCraft 1.8 program. Modeling was performed using the density functional theory (DFT) method, the B3LYP functional [24,25], and the 6-31G* basis set, which is consistent with previous studies [26]. The influence of the solvent (water) was taken into account in the self-consistent reaction field (SCRF) model [19,27].…”