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Volumn 125, Issue 45, 2003, Pages 13776-13783

"Electromers" of the Tetramethyleneethane Radical Cation and Their Nonexistence in the Octamethyl Derivative: Interplay of Experiment and Theory

Author keywords

[No Author keywords available]

Indexed keywords

DELOCALIZED STRUCTURES;

EID: 16744366259     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja037252v     Document Type: Article
Times cited : (19)

References (45)
  • 8
    • 0242475498 scopus 로고    scopus 로고
    • note
    • 1u state has two directions of negative curvature, one of them corresponding to the twisting deformation.
  • 15
    • 0242392154 scopus 로고
    • We had previously encountered a case of a bisallylic radical cation, bicyclo-[3.3.0]octa-2.6-diene-4,8-diyl, with a similar CR transition involving the bonding and the antibonding combination of allyl-NBMOs (Bally, T.; Truttmann, L.; Dai, S.; Wang, J. T.; Williams, F. Chem. Phys. Lett. 1993, 212, 141). However, in that case, the molecular framework did not allow for a relaxation of the excited state to a new ground-state equilibrium structure with the same atomic connectivities but with a distinct electronic structure (instead, this species underwent photoinduced tautomerization).
    • (1993) Chem. Phys. Lett. , vol.212 , pp. 141
    • Bally, T.1    Truttmann, L.2    Dai, S.3    Wang, J.T.4    Williams, F.5
  • 21
    • 0242392152 scopus 로고    scopus 로고
    • note
    • 2 by 0.2). In ROHF, the preference for localized states is smaller, but this method is useless in the present context, because it ignores spin polarization and, in addition, shows pronounced symmetry breaking in the localized state. A way out of this impasse would be to use CASSCF (which models spin polarization through an admixture of singly excited states). We did indeed carry out such calculations, but they also invariably resulted in localized structures, in disagreement with experiment for the parent radical cation.
  • 22
    • 0242559225 scopus 로고    scopus 로고
    • note
    • The parent system is small enough that it could possibly be treated by coupled cluster methods, but even those methods would probably find it difficult to strike the right balance between the opposing forces, given the dubious quality of the one-electron wave functions on which they would have to be based in the present case.
  • 26
    • 24444467644 scopus 로고    scopus 로고
    • Unpublished results
    • The difference in the endo/exo coupling constants predicted by B3LYP is usually too large, but the average value is predicted correctly within <0.1 mT in allylic radicals carrying methyl groups (Müller, B.; Bally, T. Unpublished results).
    • Müller, B.1    Bally, T.2
  • 29
    • 0242559226 scopus 로고
    • Lund, A., Shiotani, M., Eds.; Kluwer Academic Publishers: Dordrecht, Germany
    • Bally, T. In Radical Ionic Systems; Lund, A., Shiotani, M., Eds.; Kluwer Academic Publishers: Dordrecht, Germany, 1991; pp 19-20.
    • (1991) Radical Ionic Systems , pp. 19-20
    • Bally, T.1
  • 43
    • 0002438497 scopus 로고
    • World Scientific Publishing Company: Singapore
    • Andersson, K.; Roos, B. O. Modern Electronic Structure Theory; World Scientific Publishing Company: Singapore, 1995; Vol. Part 1, Vol. 2; p 55.
    • (1995) Modern Electronic Structure Theory , vol.2 , Issue.PART 1 , pp. 55
    • Andersson, K.1    Roos, B.O.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.