Search results for "Hydroperoxyl"

showing 3 items of 3 documents

Benchmark Thermochemistry of the Hydroperoxyl Radical

2004

A theoretical estimation of the enthalpy of formation for the hydroperoxyl radical is presented. These results are based on CCSD(T)/aug-cc-pCV5Z calculations extrapolated to the basis-set limit with additional corrections. Anharmonic vibrational zero-point energies, scalar relativistic, spin -orbit coupling, and diagonal BornOppenheimer corrections are further used to correct the extrapolated term energies, as well as various empirical corrections that account for correlation effects not treated at the CCSD(T) level. We estimate that ¢fH° ) 3.66 ( 0.10 kcal mol -1 (¢fH° ) 2.96 ( 0.10 kcal mol -1 ) using several reaction schemes. Significantly, it appears to be necessary to include effects o…

CouplingQuantitative Biology::BiomoleculesChemistryScalar (mathematics)AnharmonicityDiagonalchemistry.chemical_compoundHydroperoxylThermochemistryLimit (mathematics)Physics::Chemical PhysicsPhysical and Theoretical ChemistryAtomic physicsSpin-½The Journal of Physical Chemistry A
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A kinetic model for the oxidation of benzenethiol catalyzed by the [MoVIO2(O2CC(S)(C6H5)2)2]2− complex intercalated in a Zn(II)–Al(III) layered doubl…

2009

Abstract The heterogeneous oxidation of benzenethiol catalyzed by the dianionic bis(2-sulfanyl-2,2-diphenylethanoxycarbonyl) dioxomolybdate (VI) complex intercalated into a Zn(II)–Al(III) layered double hydroxide (LDH) host have been investigated under aerobic conditions. The kinetics of the system has been analysed in detail. In ethanol, the benzenethiol is cleanly oxidized to diphenyl disulfide in the acidic media provided by the protonic resin Amberlite IR-120(H). The reaction is second-order in benzenethiol, and the apparent rate coefficient has been found to be proportional to the catalyst weight and inversely proportional to the initial concentration of the substrate. A catalytic cycl…

Diphenyl disulfideProcess Chemistry and TechnologyInorganic chemistryComproportionationRate-determining stepMedicinal chemistryCatalysisCatalysischemistry.chemical_compoundchemistryCatalytic cycleHydroperoxylOxidation stateHydroxidePhysical and Theoretical ChemistryJournal of Molecular Catalysis A: Chemical
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Calculation of the rate constants for hydrogen abstraction reactions by Hydroperoxyl radical from Methanol, and the investigation of stability of CH3…

2020

Abstract Master equation (ME) with Lennard-Jones potential utilized to simulate the collision between CH3OH and HO2 radical in the presence of bath gas. The reaction mechanism explored through the lowest doublet potential energy surface at CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ level of theory that is barrierless and forms shallow energized intermediate at the entrance channel. The investigation of the fractional population showed that lifetime of CH3OH.HO2 intermediate (INT*) is fairly short due to its shallow depth, and at the low temperature, most reaction takes place by re-dissociation back to reactants and also when the pressure is high enough, the INT* is thermalized and comes into eq…

Reaction mechanismeducation.field_of_study010304 chemical physicsChemistryPopulationThermodynamics010402 general chemistryCondensed Matter PhysicsHydrogen atom abstraction01 natural sciencesBiochemistry0104 chemical scienceschemistry.chemical_compoundReaction rate constantHydroperoxyl0103 physical sciencesPotential energy surfaceMaster equationPhysical and Theoretical ChemistryeducationEquilibrium constantComputational and Theoretical Chemistry
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