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Volumn 125, Issue 5, 2003, Pages 1293-1308

Noninnocence of the ligand glyoxal-bis(2-mercaptoanil). The electronic structures of [Fe(gma)]2, [Fe(gma)(py)]·py, [Fe(gma)(CN)]1-/0, [Fe(gma)I], and [Fe(gma)(PR3)n] (n = 1, 2). Experimental and theoretical evidence for "excited state" coordination

Author keywords

[No Author keywords available]

Indexed keywords

RADICAL TRIANION;

EID: 0037419799     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja021123h     Document Type: Article
Times cited : (108)

References (79)
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    • Siemens, Analytical X-ray Instruments, Inc.
    • ShelXTL V.5, Siemens Analytical X-ray Instruments, Inc., 1994.
    • (1994) ShelXTL V.5
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    • Basis sets were obtained from the ftp server of the quantum chemistry group at the university of Karlsruhe (Germany) under
    • Basis sets were obtained from the ftp server of the quantum chemistry group at the university of Karlsruhe (Germany) under http://www.chemie.uni-karlsruhe.de/PC/TheoChem/.
  • 43
    • 0004015421 scopus 로고    scopus 로고
    • Espoo, Finland, obtained from
    • Laaksonen, L. The gOpenMol effort, Version 1.4, Espoo, Finland, 2000, obtained from http://www.csc.fi/∼laaksone/gopenmol/gopenmol.html.
    • (2000) The gOpenMol Effort, Version 1.4
    • Laaksonen, L.1
  • 46
    • 0345891711 scopus 로고    scopus 로고
    • note
    • B at 298 K).
  • 51
    • 0001121799 scopus 로고    scopus 로고
    • Sellmann, D.; Kleine-Kleffmann, U.; Zapf, L.; Huttner, G.; Zsolnai, L. J. Organomet. Chem. 1984, 263, 321. Sellmann, D.; Emig, S:; Heinemann, F. W.; Knoch, F. Angew. Chem. 1997. 109, 1250.
    • (1997) Angew. Chem. , vol.109 , pp. 1250
    • Sellmann, D.1    Emig, S.2    Heinemann, F.W.3    Knoch, F.4
  • 63
    • 0346522504 scopus 로고    scopus 로고
    • note
    • Note that orbital energy differences are more meaningful in DFT calculations that do not incorporate the Hartree-Fock exchange compared to those calculated with hybrid functionals or the Hartree-Fock method. In HF calculations the virtual orbitals "see" and N electron system instead of a N - 1 electron system as it should be. Therefore all of these orbitals are too high in energy and are too diffuse. To the extent that HF exchange is incorporated into hybrid DFT, this shortcoming is "inherited" from HF in these functionals. There are no observables that can be meaningfully related to the orbital energy differences in either case. By contrast, for "pure" functionals the virtual orbitals are appropriate and the orbital energy differences are well-defined zero-order approximations for excitation energies.
  • 70
    • 0347152837 scopus 로고    scopus 로고
    • note
    • The shapes of the MO's in Figure 11 do not resemble the textbook-like d-orbitals well. This is a result of the localization procedure used to "separate" the metal from the ligand orbitals. The canonical orbitals are very strongly mixed and are not illuminating in indicating the electronic configuration of the iron. The resulting description we develop here is nevertheless valid.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.