Jump to main content
Jump to site search


Time-dependent DFT study of K-edge spectra for vanadium and titanium complexes: Effects of chloride ligands on pre-edge features

Abstract

X-ray absorption near edge structure (XANES) of vanadium and titanium complexes were investigated with time-dependent density functional theory (TDDFT). In particular, observed characteristic K-edge features in the presence of chloride ligands were assigned. Although TDDFT includes a large systematic error attributed to 1s core energy levels of transition metals, pre-edge spectral shapes could be reproduced by a simple energy shift in the calculated excitation energies. The doublet peak in the pre-edge region was assigned to dipole-allowed transitions from 1s to 3d+4p hybridized orbitals, while a characteristic shoulder peak in the chloride complex was assigned to excitations of chloride 4p orbitals. A similar but weak absorption band was computed for the methyl complex as excitations to C-H σ* orbitals. However, because these excitations were highly dependent on the direction of the C-H bonds, the shoulder peak was not experimentally observed because of methyl free rotation. Hence, the intensity of the shoulder peak was proportional to the number of chloride ligands unless other ligand contributes to this energy region and, therefore, could be used to detect the presence or absence of chloride ligands in unknown compounds, such as reaction intermediates.

Back to tab navigation

Supplementary files

Publication details

The article was received on 30 Oct 2019, accepted on 02 Dec 2019 and first published on 03 Dec 2019


Article type: Paper
DOI: 10.1039/C9CP05891E
Phys. Chem. Chem. Phys., 2019, Accepted Manuscript

  •   Request permissions

    Time-dependent DFT study of K-edge spectra for vanadium and titanium complexes: Effects of chloride ligands on pre-edge features

    J. Yi, N. Nakatani, K. Nomura and M. Hada, Phys. Chem. Chem. Phys., 2019, Accepted Manuscript , DOI: 10.1039/C9CP05891E

Search articles by author

Spotlight

Advertisements