The Cl K-edge spectra of a series of transition metal tetrachloride complexes (CuIICl42-, NiIICl42-, CoIICl42-, FeIICl42- and FeIIICl4-) have been simulated using a multi-configurational RASSCF/RASSI protocol. The influence of basis set, solvation and especially the active space choice has been systematically investigated. The separability of the contributions of the different Cl ligands was explored by including only one Cl in the active space at a time. This approach is faster than including all of the ligands and it is especially useful for heavy elements in reducing the number of irrelevant transitions to be computed. The utility of this approach was demonstrated by computing the C K-edge spectra of ferrocene (FeCp2*). Our results show good agreement between the calculated spectra and the relative experimental energies and intensities.Furthermore, the multiconfigurational nature of our protocol will allow us to compute the Cl K-edge spectra of uranium tetrachloride complexes with low uranium oxidation states, for which other approaches, e.g., time dependent density functional theory, fail.

Multiconfigurational calculations of ligand K-edge X-ray absorption spectra

245th National Meeting (2013)

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