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Ab-initio CI calculations for 3d transition metal L2,3 X-ray absorption spectra of TiCl4 and VOCl3

Hidekazu Ikeno1, Frank M F de Groot1 and Isao Tanaka2,3

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X-ray-absorption near-edge structures (XANES) at the transition metal (TM) L2,3-edge of TiCl4 and VOCl3 are calculated by the all-electron configuration interaction (CI) method using fully-relativistic molecular spinors with density functional theory (DFT). The electronic excitation from molecular spinors mainly composed of ligand p atomic spinors to those of TM-3d spinors, i.e., the charge transfer, is included by taking additional electronic configurations in the CI. The effects of the ligand field and the charge transfer on the TM-L2,3 XANES are investigated by an ab-intio method. The reduction of inter-electron interaction due to the covalent bonding between TM and ligand atoms has been found. The contribution of charge transferred configuration is small at the initial state of TM-L2,3 XANES while the significant amount of charge transferred configuration is found at the final states. The spectral shapes of TM-L2,3 XANES of both TiCl4 and VOCl3 are strongly modified by the charge transfer effects.


PACS

33.20.Rm X-ray spectra

31.15.V- Electron correlation calculations for atoms, ions and molecules

31.15.E- Density-functional theory

34.70.+e Charge transfer

33.15.Fm Bond strengths, dissociation energies

31.30.J- Relativistic and quantum electrodynamic (QED) effects in atoms, molecules, and ions

Subjects

Atomic and molecular physics

Computational physics

Dates

Issue 1 (2009)



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