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Volumn 43, Issue 8, 2004, Pages 2597-2610

DFT and Metal-Metal Bonding: A Dys-Functional Treatment for Multiply Charged Complexes?

Author keywords

[No Author keywords available]

Indexed keywords

METAL COMPLEX; TRANSITION ELEMENT;

EID: 4043107344     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic034525e     Document Type: Article
Times cited : (49)

References (162)
  • 9
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    • Earnshaw, A.; Lewis, J. 1961, 396
    • Earnshaw, A.; Lewis, J. 1961, 396.
  • 33
    • 85046387833 scopus 로고
    • Brosset, C. Nature 1935, 135, 874.
    • (1935) Nature , vol.135 , pp. 874
    • Brosset, C.1
  • 94
    • 16544373855 scopus 로고    scopus 로고
    • note
    • 95 (FT98: V-V ∼2.93 Å), Krieger-Chen-Iafrate-Savin96 (KCIS; V-V ∼ 2.96 Å), the combination of Perdew-Kurth-Zupan-Blaha exchange97,98 and KCIS correlation96 (PKZBx-KCIScor; V-V ∼ 2.99 Å), and the (unpublished) modified KCIS energy functional (modK-CIS; V-V ∼ 3.02 Å). Several other meta-GGAs delivered apparently poorer performance in this instance, with V-V separations between 3.13 and 3.20 Å representing a significant overestimation of the experimental metal-metal distance.
  • 122
    • 16544374598 scopus 로고    scopus 로고
    • note
    • 6. None of the identified best-performing meta-GGAs for the vanadium complex did well in this instance, with better matches provided by Filatov-Thiel 97123 (FT97) and Becke-Tsuneda-Suzumura-Hirao76,124 (BOP) both yielding Mo-Mo ∼ 2.90 Å.
  • 147
    • 16544382134 scopus 로고    scopus 로고
    • Smith, P. W. University College: London, 1962
    • Smith, P. W. University College: London, 1962.
  • 150
    • 16544363320 scopus 로고    scopus 로고
    • note
    • 3-. In this instance, to compensate for the structural sensitivity to coulombic effects, we performed linear transits using VWN+B-LYP, PBE, and B-LYP representing methods identified from our neutral and singly charged complex calculations as, respectively, overbinding, approximately "correct", and underbinding. In the resulting meta-GGA single-point calculations only the FT97 method123 performed well, with Mo-Mo ∼ 2.95 Å when VWN+B-LYP was used to provide the geometries, and the xc potential, for the meta-GGA "scan", and Mo-Mo ∼ 2.85 Å when either PBE or B-LYP was used as the underlying DFT method for which the meta-GGA energies were evaluated. For this species, all methods using the KCIS correlation functional96 collapsed as the Mo-Mo distance was decreased, while other meta-GGAs assessed consistently overestimated Mo-Mo with values of 3.4 Å or larger. The inconsistency seen with the various meta-GGAs for the three compounds assessed94,122 indicates, at least, that none of these methods can be seen as an especially promising substitute for the DFT methods for which broken-symmetry calculations are currently feasible.
  • 151
    • 16544387055 scopus 로고    scopus 로고
    • note
    • 3-, it was judged that attempting B3-LYP optimizations in broken symmetry for such species would be prohibitively computationally expensive.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.