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Por favor, use este identificador para citar o enlazar este ítem: http://repositoriodigital.ipn.mx/handle/123456789/10637
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dc.creatorValverde Aguilar, Guadalupe-
dc.creatorWang, Xianghuai-
dc.creatorPlummer, Edward-
dc.creatorLockard, Jenny V.-
dc.creatorZink, Jeffrey I.-
dc.creatorLuo, Yun-
dc.creatorWeaver, Michael N.-
dc.creatorNelsen, Stephen F.-
dc.date2012-03-15T19:39:22Z-
dc.date2012-03-15T19:39:22Z-
dc.date2008-
dc.date.accessioned2013-01-16T08:40:21Z-
dc.date.available2013-01-16T08:40:21Z-
dc.date.issued2013-01-16-
dc.identifier1089-5639-
dc.identifierhttp://hdl.handle.net/123456789/116-
dc.identifier.urihttp://www.repositoriodigital.ipn.mx/handle/123456789/10637-
dc.descriptionAbsorption spectra for 2,3-diaryl-2,3-diazabicyclo[2.2.2]octane radical cations (2(X)•+) and for their monoaryl analogues 2-tert-butyl-3-aryl-2,3-diazabicyclo[2.2.2]octane radical cations (1(X)•+) having para chloro, bromo, iodo, cyano, phenyl, and nitro substituents are reported and compared with those for the previously reported 1- and 2(H)•+ and 1- and 2(OMe)•+. The calculated geometries and optical absorption spectra for 2(Cl)•+ demonstrate that p-C6H4Cl lies between p-C6H4OMe and C6H5 in its ability to stabilize the lowest energy optical transition of the radical cation, which involves electron donation from the aryl groups toward the π*(NN)+-centered singly occupied molecular orbital of 2(X)•+. Resonance Raman spectral determination of the reorganization energy for their lowest energy transitions (λv sym) increase in the same order, having values of 1420, 5300, and 6000 cm-1 for X ) H, Cl, and OMe, respectively. A neighboring orbital analysis using Koopmans-based calculations of relative orbital energies indicates that the diabatic aryl π-centered molecular orbital that interacts with the dinitrogen π system lies closest in energy to the bonding π(NN)-centered orbital and has an electronic coupling with it of about 9200 ( 600 cm-1, which does not vary regularly with electron donating power of the X substituent.-
dc.languageen-
dc.publisherJournal of Physical Chemistry A-
dc.subjectResonance Raman-
dc.subjectAbsorption-
dc.titleTuning Aryl, Hydrazine Radical Cation Electronic Interactions Using Substitutent Effects-
dc.typeArticle-
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