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Volumn 128, Issue 22, 2006, Pages 7335-7345

Origin of trans-bent geometries in maximally bonded transition metal and main group molecules

Author keywords

[No Author keywords available]

Indexed keywords

ELECTRON ENERGY LEVELS; HYDROGENATION; MOLECULAR STRUCTURE; MOLYBDENUM; PROBABILITY DENSITY FUNCTION; TUNGSTEN;

EID: 33744930113     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja060992u     Document Type: Article
Times cited : (90)

References (66)
  • 8
    • 33744936659 scopus 로고    scopus 로고
    • Cotton, F. A., Murrillo, C. A., Walton, R. A., Eds.: Springer Science and Business Media: New York
    • Cotton, F. A. In Multiple Bonds between Metal Atoms: Cotton, F. A., Murrillo, C. A., Walton, R. A., Eds.: Springer Science and Business Media: New York, 2005; p 707.
    • (2005) Multiple Bonds between Metal Atoms , pp. 707
    • Cotton, F.A.1
  • 9
    • 33744943900 scopus 로고    scopus 로고
    • note
    • We wish to distinguish "shared" electrons of significant two-center (2c) bonding from "unshared" electrons of primarily one-center (1c) nonbonding character. Paired electrons of the latter type are merely identified as "antiferromagnetically coupled nonbonded (diradical) pairs". Although a sharp distinction between 2c bond and 1c lone-particle character is somewhat arbitrary, the NBO criterion (>5% amplitude at each center for a 2c bond) usually draws this distinction in a chemically reasonable way.
  • 41
    • 33744946145 scopus 로고    scopus 로고
    • note
    • All computations reported here were performed with the Jaguar 5.5 electronic structure package and the NBO 5.0 program. Unless otherwise stated, electronic structures were computed using the B3LYP functional with the lacv3p++** basis set, including effective core potentials for elements beyond the second period. Following geometry optimizations, vibrational frequencies were computed to assess the nature of the stationary point. Initial guesses for broken-symmetry calculations were generated using the multiplicity and formal charge features for transition metal fragments that are part of the Jaguar code.
  • 42
    • 33744926771 scopus 로고    scopus 로고
    • note
    • IIπ, to indicate unconventional bond orbitals. The first part of the symbol indicates the atomic orbitals used by M to make the bonding hybrid (e.g., s- and p-orbitals), the superscripted symbol evokes a special quality of the orbital (e.g., II represents the tilted orientations of the hybrid with respect to the internuclear axis), and the last symbol represents the most closely related conventional orbital (e.g., π).
  • 43
    • 33744932792 scopus 로고    scopus 로고
    • note
    • Note that the energies of antibonding NBOs, like those of virtual MOs, have problematic physical significance due to the curious "self- repulsion" feature of SCF theory. Nevertheless, these antibond energies are the correct quantities for evaluating perturbative "splittings" of the type considered here.
  • 50
    • 33744915648 scopus 로고    scopus 로고
    • note
    • The normal-valent 12e Lewis-like species will often be modified by coordinate additions, as described later in this section.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.