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Volumn 369, Issue 1-3, 1996, Pages 39-52

Distortive properties of σ- and π-electrons and aromaticity: A semiempirical localized molecular orbital approach

Author keywords

Aromaticity; Benzene; Cyclobutadiene; Electronic delocalization; Hexatriene; Localized molecular orbital

Indexed keywords


EID: 0011681032     PISSN: 01661280     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0166-1280(96)04599-X     Document Type: Article
Times cited : (8)

References (106)
  • 41
  • 64
    • 85087322135 scopus 로고
    • For two recent, readable introductions to the LMO approach, see: (a) R.B. Martin, J. Chem. Educ., 65 (1988) 668.
    • (1988) J. Chem. Educ. , vol.65 , pp. 668
    • Martin, R.B.1
  • 78
    • 36849104700 scopus 로고
    • Due to the accompanying decrease in the electronic kinetic energy. See: (a) J. Feinberg and K.J. Ruedenberg, J. Chem. Phys., 54 (1971) 1495.
    • (1971) J. Chem. Phys. , vol.54 , pp. 1495
    • Feinberg, J.1    Ruedenberg, K.J.2
  • 79
    • 0003849697 scopus 로고
    • O. Chalvet, R. Daudel, S. Diner and J.-P. Malrieu, Eds., Reidel, Dordrecht
    • (b) K. Ruedenberg, in: O. Chalvet, R. Daudel, S. Diner and J.-P. Malrieu, Eds., Localization and Delocalization in Quantum Chemistry, Vol. 1, Reidel, Dordrecht, 1975. For an interpretation of HMO energies and aromaticity in terms of electronic kinetic energies, see:
    • (1975) Localization and Delocalization in Quantum Chemistry , vol.1
    • Ruedenberg, K.1
  • 86
    • 0042871403 scopus 로고    scopus 로고
    • note
    • Alternant hydrocarbons can be defined as those conjugated unsaturated systems which are either acyclic or do not contain an odd-membered ring; see Ref. [3b].
  • 88
    • 0042370282 scopus 로고    scopus 로고
    • note
    • This relationship does not hold in general for in general for non-alternant hydrocarbons, since the π-LMOs of three-and seven-membered rings are more delocalized (and those of five-membered rings are more localized) than the corresponding acyclic reference structure π-LMOS.
  • 90
    • 0042871404 scopus 로고    scopus 로고
    • note
    • N is also partitioned into σ-and π-components, according to the formal number of σ-and π-electrons on each atomic center. This approach has been criticised however, on the ground that delocalization is an electronic effect and is therefore intrinsically different from nuclear repulsions; see Ref. [10b].
  • 99
    • 0041368593 scopus 로고    scopus 로고
    • See Ref. [3c], p. 39
    • See Ref. [3c], p. 39.
  • 100
    • 33751158819 scopus 로고
    • For recent calculations of the TRE of benzene, see Refs. [11b, 12d] and Y. Mo, W. Wu and O. Zhang, J. Phys. Chem., 98 (1994) 10048.
    • (1994) J. Phys. Chem. , vol.98 , pp. 10048
    • Mo, Y.1    Wu, W.2    Zhang, O.3
  • 104
    • 0041869344 scopus 로고    scopus 로고
    • note
    • 2h symmetry point group) always lead to a maximum value of the localization sum defined by Eq. (11); see Ref. [34].
  • 105
    • 0042370279 scopus 로고    scopus 로고
    • note
    • CC LMOs of benzene, which stands in sharp contrast with that of the corresponding LMOs in singlet cyclobutadiene and in 1,3,5-hexatriene, could be indicative, as suggested by Dewar [42], of the presence of σ-aromaticity on the six-membered carbon-carbon ring.
  • 106
    • 0021757419 scopus 로고
    • see also Ref. [3c], ch. 7
    • M.J.S. Dewar, J. Am. Chem. Soc. 106 (1984) 669; see also Ref. [3c], ch. 7.
    • (1984) J. Am. Chem. Soc. , vol.106 , pp. 669
    • Dewar, M.J.S.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.