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Volumn 127, Issue 2, 2005, Pages 667-674

Metal and ligand K-edge XAS of organotitanium complexes: Metal 4p and 3d contributions to pre-edge intensity and their contributions to bonding

Author keywords

[No Author keywords available]

Indexed keywords

CALCULATIONS; CATALYST ACTIVITY; CORRELATION METHODS; HOMOPOLYMERIZATION; MATHEMATICAL MODELS; METALS;

EID: 12944298284     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja044827v     Document Type: Article
Times cited : (135)

References (53)
  • 31
    • 12944312988 scopus 로고    scopus 로고
    • Stanford Synchrotron Radiation Laboratory, Stanford Linear Accelerator Center. Stanford University, Stanford, CA 94309
    • George, G. N. Stanford Synchrotron Radiation Laboratory, Stanford Linear Accelerator Center. Stanford University, Stanford, CA 94309.
    • George, G.N.1
  • 40
    • 0033437855 scopus 로고    scopus 로고
    • In these complexes, dipole and quadrupole based transitions are not shifted in energy. This is in contrast to studies on infinite lattice structures were 3d-3d hybridization between neighboring Ti atoms is thought to occur. [Cabaret, D.; Joly, Y.; Renevier, H.; Natoli, C. R. J. Synch. Rad. 1999, 6, 258 and Shirley, E. L. J. Electron Spectrosc. Relat. Phenom. 2004, 135, 77.] The present study examines molecular complexes where extended lattice interactions do not complicate the bonding description.
    • (1999) J. Synch. Rad. , vol.6 , pp. 258
    • Cabaret, D.1    Joly, Y.2    Renevier, H.3    Natoli, C.R.4
  • 41
    • 2342450455 scopus 로고    scopus 로고
    • In these complexes, dipole and quadrupole based transitions are not shifted in energy. This is in contrast to studies on infinite lattice structures were 3d-3d hybridization between neighboring Ti atoms is thought to occur. [Cabaret, D.; Joly, Y.; Renevier, H.; Natoli, C. R. J. Synch. Rad. 1999, 6, 258 and Shirley, E. L. J. Electron Spectrosc. Relat. Phenom. 2004, 135, 77.] The present study examines molecular complexes where extended lattice interactions do not complicate the bonding description.
    • (2004) J. Electron Spectrosc. Relat. Phenom. , vol.135 , pp. 77
    • Shirley, E.L.1
  • 42
    • 12944269220 scopus 로고    scopus 로고
    • note
    • 4. which demonstrate that creation of a ls core hole changes the d-orbital energy splittings by less than 0.2 eV and although the d-character is reduced by x0.88, the relative intensities are essentially unchanged. A VBCI analysis which reproduces the ground-state parameters and allows for a Q of 4 eV for relaxation gives less than 10% intensity redistribution into shake-up satellites. Shake-up satellites are also not observed experimentally.
  • 46
    • 12944272312 scopus 로고    scopus 로고
    • note
    • From Table 2, the covalency is 32% per Ti-Cl bond or a total Cl 3p covalency of 96% over the five metal 3d Orbitals. Using the relative intensity ratios of the two pre-edge peaks (Table 2), it is determined that 62% Cl 3p character will be in the three lowest energy d-orbitals and 34% will be in the two highest energy d-orbitals.
  • 47
    • 12944328164 scopus 로고    scopus 로고
    • note
    • 4.
  • 53
    • 12944312989 scopus 로고    scopus 로고
    • note
    • 2 = 2.0 eV gives a metal d-based ground state with 75% 3d character, 20% Cl 3p character, and 5% 4p mixing.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.