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Theoretical study of the gas-phase thermolysis of 3-methyl-1,2,4,5- tetroxane

dc.contributor.authorProfeta M.I.
dc.contributor.authorRomero J.M.
dc.contributor.authorJorge N.L.
dc.contributor.authorGrand A.
dc.contributor.authorHernández-Laguna A.
dc.date.accessioned2020-09-02T22:25:58Z
dc.date.available2020-09-02T22:25:58Z
dc.date.issued2014
dc.identifier10.1007/s00894-014-2224-6
dc.identifier.citation20, 6, -
dc.identifier.issn16102940
dc.identifier.urihttps://hdl.handle.net/20.500.12728/5853
dc.descriptionCyclic organic peroxides are a broad and highly sought-after class of peroxide compounds that present high reactivity and even explosive character. The unusually high reactivity of these peroxides can generally be attributed to the rupture of O-O bonds. Cyclic diperoxides are a very interesting series of substituted compounds in which tetroxane is the most prominent member. Gas-phase thermolysis of the simplest substituted member of the series [3-methyl-1,2,4,5-tetroxane or methylformaldehyde diperoxide (MFDP)] has been observed to yield one acetaldehyde, one formaldehyde, and one oxygen molecule as reaction products. DFT at the 6-311+G**level of theory using the BHANDHLYP correlation-exchange functional was applied via the Gaussian09 program to calculate the critical points of the potential energy surface (PES) of this reaction. Equatorial and axial isomers were studied. The singlet state PES of MFDP was calculated, and an open diradical structure was found to be the first intermediate in a stepwise reaction. Two PESs were subsequently obtained: singlet state (S) and triplet state (T) PESs. After that, two alternative stepwise reactions were found to be possible: 1) one in which either an acetaldehyde, or 2) formaldehyde molecule is initially formed. For second one, exothermic reactions were observed for both the S and T PESs. The reaction products include a oxygenmolecule in either S or T state, with the T reaction being the most exothermic. When calculations were performed at the CASSCF(10,10)/6-311+ G**level, spin-orbit coupling permitted S to Tcrossing at the open diradical intermediate stage, a non-adiabatic reaction was observed, and lower activation energies and higher exothermicity were generally seen for the T PES than for the S PES. These results were compared with the corresponding results for tetroxane. The spin-orbit coupling of MFDP and tetroxane yielded identical values, so it appears that the methyl substituent does not have any effect on this coupling. © Springer-Verlag 2014.
dc.language.isoen
dc.publisherSpringer Verlag
dc.subject3-Methyl-1,2,4,5-tetroxane/methylformaldehyde diperoxide
dc.subjectCyclic diperoxides
dc.subjectDFT
dc.subjectEquatorial and axial isomers
dc.subjectGas-phase thermolysis reaction
dc.subjectPotential energy surface
dc.subjectReaction mechanisms
dc.subject3 methyl 1,2,4,5 tetroxane
dc.subjectacetaldehyde
dc.subjectformaldehyde
dc.subjectheterocyclic compound
dc.subjectmethylformaldehyde diperoxide
dc.subjectoxygen
dc.subjectperoxide
dc.subjectunclassified drug
dc.subject3-methyl-1,2,4,5-tetroxane
dc.subjectgas
dc.subjecttetraoxane derivative
dc.subjectarticle
dc.subjectenergy
dc.subjectgas
dc.subjectisomer
dc.subjectmolecular dynamics
dc.subjectpriority journal
dc.subjecttemperature
dc.subjecttheoretical study
dc.subjectthermolysis
dc.subjectchemical model
dc.subjectchemical structure
dc.subjectchemistry
dc.subjectcomparative study
dc.subjectcomputer simulation
dc.subjectenergy transfer
dc.subjectexplosion
dc.subjectgas
dc.subjectAcetaldehyde
dc.subjectComputer Simulation
dc.subjectEnergy Transfer
dc.subjectExplosions
dc.subjectFormaldehyde
dc.subjectGases
dc.subjectModels, Chemical
dc.subjectModels, Molecular
dc.subjectMolecular Structure
dc.subjectOxygen
dc.subjectTemperature
dc.subjectTetraoxanes
dc.titleTheoretical study of the gas-phase thermolysis of 3-methyl-1,2,4,5- tetroxane
dc.typeArticle


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