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Volumn 11, Issue 17, 2005, Pages 4921-4934

Valence shell charge concentrations at pentacoordinate d0 transition-metal centers: Non-VSEPR structures of Me2NbCl3 and Me3NbCl2

Author keywords

Charge density; Gas electron diffraction; Niobium

Indexed keywords

CARRIER CONCENTRATION; CHEMICAL BONDS; CRYSTAL ATOMIC STRUCTURE; DISCRETE FOURIER TRANSFORMS; ELECTRIC CHARGE; ELECTRON DIFFRACTION; ELECTRONIC STRUCTURE; MOLECULAR STRUCTURE; MOLECULAR VIBRATIONS;

EID: 24344445290     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200400808     Document Type: Article
Times cited : (38)

References (96)
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    • G. S. McGrady, A. J. Downs, unpublished results
    • G. S. McGrady, A. J. Downs, unpublished results.
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    • E. D. Glendening, A. E. Reed, J. E. Carpenter, F. Weinhold, NBO Version 3.1; we note that the Kohn-Sham method employed in our study at the B3LYP/DZVP level is based on a fictitious reference system of non-interacting electrons (the non-interacting system), so that there is no DF wavefunction in a strict sense. However, it has been demonstrated that Kohn-Sham orbitals resemble orbitals computed at the Hartree-Fock level; see ref. [14a] for further information. Hence they can be employed here in our qualitative MO discussions employing the NBO concept. See also: a) E. J. Baerends, O. V. Gritsenko, J. Phys. Chem. A 1997, 101, 5383-5403;
    • (1997) J. Phys. Chem. A , vol.101 , pp. 5383-5403
    • Baerends, E.J.1    Gritsenko, O.V.2
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    • note
    • 3v symmetry.
  • 70
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    • 3, However, selection of basis sets of larger flexibility in valence space or choice of more appropriate theoretical models to account for the electron correlation leads to much better agreement between experimental and calculated structural parameters. For example employing the CCSD method and replacing our standard DZVP basis set at the niobium atom by the Stuttgart relativistic, small core ECP basis set (D. Andrae, U. Haeussermann, M. Dolg, H. Stoll, H. Preuss, Theor. Chim. Acta 1990, 77, 123-141) results in a CNbC angle of 118.7° in much better agreement with experiment; see Supporting Information S6c for further calculations.
    • (1990) Theor. Chim. Acta , vol.77 , pp. 123-141
    • Andrae, D.1    Haeussermann, U.2    Dolg, M.3    Stoll, H.4    Preuss, H.5
  • 74
    • 24344467432 scopus 로고    scopus 로고
    • note
    • Where necessary, we will denote hereafter these ligand-induced charge concentrations trans-LICCs or cis-LICCs with respect to their location in the valence shell of the metal and to the corresponding metal-ligand bonding domains.
  • 76
    • 24344443681 scopus 로고    scopus 로고
    • note
    • +.
  • 77
    • 24344505425 scopus 로고    scopus 로고
    • note
    • Our test calculations indicated that an additional contribution to the valence density from the superposition of partially occupied antibonding NBOs was irrelevant to the polarization pattern at the TM atom (see Supporting Information).
  • 78
    • 24344507687 scopus 로고    scopus 로고
    • note
    • This is not a major complication or drawback with the Laplacian function. In any event, the essential features of the charge density, namely the localization of valence charge concentrations, are sufficiently revealed by the Laplacian of the total charge density.
  • 79
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    • note
    • 5, respectively, which stress the more covalent character of the Ca-H bond.
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    • note
    • z2-type AO.
  • 85
    • 0002473993 scopus 로고    scopus 로고
    • The AIM method provides an elegant concept to partition the total charge density in real space by zero-flux surfaces into atomic basins. This is different from our approach where the individual contribution of natural bonding orbitals (NBOs) to the total charge density is analyzed. Hence, according to the suggestions of one of our referees, the differences between the two approaches could be further specified as partitioning in real space (AIM method) versus partitioning in Hilbert space (NBO method). Indeed, the NBOs are one sequence of natural localized orbital sets that include atomic (NAO), hybrid (NHO), and (semi)localizcd molecular orbital (NLMO) sets intermediate between basis atomic orbitals (AOs) and delocalized molecular orbitals (MOs): AOs → NAOs → NHOs → NBOs → NLMOs → MOs. All these natural localized sets are complete and orthonormal, able exactly to describe any property of the state function, ψ, in Hilbert space (see F. Weinhold, C. R. Landis, Chem. Educ. Res. Pract. Eur. 2001, 2, 91-104). As a consequence, the complete set of bonding and antibonding NBOs can be employed to expand the electron density ρ(r) of ψ in a highly compact way similar to the features of natural orbitals (NOs) introduced in 1955 by Löwdin (see
    • (2001) Chem. Educ. Res. Pract. Eur. , vol.2 , pp. 91-104
    • Weinhold, F.1    Landis, C.R.2
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    • P.-O. Löwdin, Phys. Rev. 1955, 97, 1474-1489). For further discussion of the NBO method see for example
    • (1955) Phys. Rev. , vol.97 , pp. 1474-1489
    • Löwdin, P.-O.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.