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Volumn 130, Issue 33, 2008, Pages 10947-10954

Effect of spin-orbit coupling on reduction potentials of octahedral ruthenium(II/III) and osmium(II/III) complexes

Author keywords

[No Author keywords available]

Indexed keywords

OSMIUM; RUTHENIUM;

EID: 50349101356     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja800616s     Document Type: Article
Times cited : (52)

References (59)
  • 27
    • 50349092219 scopus 로고    scopus 로고
    • The choice of the minimum active space was fairly straightforward once we realized that all of the studied complexes have well-defined low-spin ground states (either doublets or singlets) with five or six valence d electrons in the three metal t2g MOs and that the two metal eg* MOs typically do not represent the lowest unoccupied MOs for complexes of second-and third-row transition metals. By adding the two metal eg* MOs to the minimum active space, we would allow for the effect of the (t 2g)n-k(eg)k configurations (k, 1-4, n, 5 or 6) on the electronic energies and wave functions of the three lowest-energy doublets while ignoring the effect of more-favorable configurations resulting from the distribution of some of the d electrons into the low-lying ligand MOs. Even if the complexes have no symmetry, the minimum active space ensures that the three near-degenerate highe
    • k configurations (k = 1-4, n = 5 or 6) on the electronic energies and wave functions of the three lowest-energy doublets while ignoring the effect of more-favorable configurations resulting from the distribution of some of the d electrons into the low-lying ligand MOs. Even if the complexes have no symmetry, the minimum active space ensures that the three near-degenerate highest occupied MOs emerge as suitable linear combinations of the five metal d atomic orbitals from the CASSCF optimization.
  • 29
    • 50349097876 scopus 로고    scopus 로고
    • Schimmelpfenning, B. AMFI Program; University of Stockholm: Stockholm, 1996.
    • Schimmelpfenning, B. AMFI Program; University of Stockholm: Stockholm, 1996.
  • 36
  • 37
    • 50349084933 scopus 로고    scopus 로고
    • Neese, F. ORCA: An ab Initio, DFT, and Semiempirical SCF-MO Package; University of Bonn: Bonn, Germany, 2007.
    • Neese, F. ORCA: An ab Initio, DFT, and Semiempirical SCF-MO Package; University of Bonn: Bonn, Germany, 2007.
  • 52
    • 0003998388 scopus 로고    scopus 로고
    • 88th ed, Lide, D. R, Ed, CRC Press: Boca Raton, FL
    • CRC Handbook of Chemistry and Physics, 88th ed.; Lide, D. R., Ed.; CRC Press: Boca Raton, FL, 2007.
    • (2007) CRC Handbook of Chemistry and Physics


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.