Interplay of Intrinsic and Environmental Effects on the Magnetic Properties of Free Radicals Issuing from H-Atom Addition to Cytosine
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- 作者：Carlo Adamo ; Marie Heitzmann ; Flora Meilleur ; Nadia Rega ; Giovanni Scalmani ; Andre Grand ; Jean Cadet ; and Vincenzo Barone
- 刊名：Journal of the American Chemical Society
- 出版年：2001
- 出版时间：July 25, 2001
- 年：2001
- 卷：123
- 期：29
- 页码：7113 - 7117
- 全文大小：75K
- 年卷期：v.123,no.29(July 25, 2001)
- ISSN：1520-5126
文摘
Possible radical reaction products issuing from H-atom addition to cytosine have been characterizedand analyzed by means of a comprehensive quantum mechanical approach including density functionalcomputations (B3LYP), together with simulation of the solvent by the polarizable continuum model (PCM),and averaging of spectroscopic properties over the most important vibrational motions. The hyperfine couplingsof the semirigid 5,6-dihydrocytos-6yl radical computed at the optimized geometry are in good agreement withtheir experimental counterparts. On the other hand, vibrational averaging is mandatory for obtaining an effectivelyplanar structure for the 5,6-dihydrocytos-5yl radical with the consequent equivalence of 
-hydrogens. Finally,only proper consideration of environmental effects restores the agreement between computed and experimentalcouplings for the base anion protonated at N3.
-hydrogens. Finally,only proper consideration of environmental effects restores the agreement between computed and experimentalcouplings for the base anion protonated at N3.