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Campo DC | Valor | Lengua/Idioma |
---|---|---|
dc.creator | Valverde Aguilar, Guadalupe | - |
dc.creator | Wang, Xianghuai | - |
dc.creator | Plummer, Edward | - |
dc.creator | Lockard, Jenny V. | - |
dc.creator | Zink, Jeffrey I. | - |
dc.creator | Luo, Yun | - |
dc.creator | Weaver, Michael N. | - |
dc.creator | Nelsen, Stephen F. | - |
dc.date | 2012-03-15T19:39:22Z | - |
dc.date | 2012-03-15T19:39:22Z | - |
dc.date | 2008 | - |
dc.date.accessioned | 2013-01-16T08:40:21Z | - |
dc.date.available | 2013-01-16T08:40:21Z | - |
dc.date.issued | 2013-01-16 | - |
dc.identifier | 1089-5639 | - |
dc.identifier | http://hdl.handle.net/123456789/116 | - |
dc.identifier.uri | http://www.repositoriodigital.ipn.mx/handle/123456789/10637 | - |
dc.description | Absorption 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.language | en | - |
dc.publisher | Journal of Physical Chemistry A | - |
dc.subject | Resonance Raman | - |
dc.subject | Absorption | - |
dc.title | Tuning Aryl, Hydrazine Radical Cation Electronic Interactions Using Substitutent Effects | - |
dc.type | Article | - |
Aparece en las colecciones: | Doctorado |
Ficheros en este ítem:
Fichero | Descripción | Tamaño | Formato | |
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JPC A_p_Cl 2008.pdf | 862.14 kB | Adobe PDF | Visualizar/Abrir |
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