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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.
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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.
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note
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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.
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12944272312
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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.
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47
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12944328164
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note
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12944312989
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note
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2 = 2.0 eV gives a metal d-based ground state with 75% 3d character, 20% Cl 3p character, and 5% 4p mixing.
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