Time-dependent density functional calculations of ligand K-edge X-ray absorption spectra

The Cl K-edge spectra of a series of metal tetrachloride complexes have been simulated using a simple TD-DFT based protocol. The influence of the chosen density functional, relativistics, basis set, and solvation has been systematically investigated. The results show that good agreement between the calculated spectra and the relative experimental energies and intensities can be achieved by using the BP86 functional with standard polarized triple-ζ basis sets (such as the TZVP basis of Ahlrichs’s and co-workers). Calculated energies and intensities are improved by using the more flexible CP(PPP) basis set on the metal atom. The inclusion of scalar-relativistic effects or solvation does not yield any significant improvement in the results. The subtleties arising from the incorporation of electric quadrupole and magnetic dipole intensity contributions into the calculations are discussed in some detail, and the contributions are shown to be negligible (∼1%) at the Cl K-edge.

The development of a protocol for time-dependent DFT calculations of ligand K-edge X-ray absorption spectra is described. The influence of the chosen density functional, relativistics, basis set, and solvation has been systematically investigated. The incorporation of electric quadrupole and magnetic dipole intensity contributions into the calculations is discussed and is found to be negligible.Figure optionsDownload as PowerPoint slide