X-ray absorption spectroscopy of VOCl3, CrO2Cl2, and MnO3Cl: an experimental and theoretical study.

X-ray absorption spectra of gas-phase VOCl(3) and CrO(2)Cl(2) have been measured in the metal L(2,3)-edge and O K-edge regions. The assignment of the spectral features is based on the relativistic two-component ZORA TDDFT approach. The calculations provide results in excellent agreement with the experimental spectra and prove the importance of including both configuration mixing and spin-orbit coupling in the theoretical description to obtain a reliable simulation of the transition metal L(2,3)-edge. The calculations are extended also to the MnO(3)Cl molecule to discuss the spectral variations along the series of the oxychlorides both in the metal L(2,3) and ligand O K spectra.