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dc.contributorWichita State University. Department of Chemistryen_US
dc.contributor.authorKombarova, Svetlana V.en_US
dc.contributor.authorIl'ichev, Yuri V.en_US
dc.identifier.citationThe Journal of organic chemistry. 2005 Jul 22; 70(15): 6074-84.en_US
dc.descriptionClick on the DOI link below to access the article (may not be free).en_US
dc.description.abstractSpin-unrestricted calculations and time-dependent DFT were used to characterize structure and reactivity of 1-methyl-8-nitronaphthalene (1) in the triplet state. Four hybrid models (B3LYP, PBE0, MPW1K, BHLYP) with significantly different amount of the exact exchange were employed. The triplet potential energy surface of 1 was mapped by using the UB3LYP and UMPW1K techniques. Both hybrid models provided qualitatively consistent pictures for the potential energy landscape. Thirty-one stationary points, of which 15 were minima, were found at the UB3LYP level of theory. Three minima corresponding to the nitro form of 1 were located on the triplet surface; just one was found for the singlet ground state. Two reaction paths leading from 1 either to a nitrite-type intermediate (2) or to the aci-form (3) were characterized. For both paths, reaction products were of diradical nature. The lower activation energy was obtained for the triplet-state tautomerization affording 3. The ground state of triplet multiplicity was predicted for two isomers of the aci-form. The triplet diradical 3 is expected to react through the thermal population of a close-lying singlet excited state. The results are discussed in relation to mechanisms of photoinduced rearrangements of peri-substituted nitronaphthalenes that can be used to develop novel photolabile protecting groups.en_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.ispartofseriesThe Journal of organic chemistryen_US
dc.relation.ispartofseriesJ. Org. Chem.en_US
dc.titleMapping the triplet potential energy surface of 1-methyl-8-nitronaphthaleneen_US
dc.coverage.spacialUnited Statesen_US
dc.description.versionpeer revieweden_US
dc.rights.holderCopyright © 2005 American Chemical Societyen_US

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