At the chlorine K-edge there is also an intense pre-edge feature for all three complexes [Fig. ]. CAM-B3LYP/ CIS spectra need a 6.7 eV shift to match the experimental peak at 2820 eV. It is most intense for TiCl 4 and decreases in intensity with the additional of each subsequent Cp ligand, a trend that is reproduced by the CAM-B3LYP/CIS calculations and arises due to decreased covalency of the Ti-Cl bond upon its replacement by a Cp ligand. For TiCpCl 3 and TiCp 2 Cl 2 there are peak splittings in the pre-edge features that were reported experimentally, arising from the splitting of the Ti(3d) e g and t 2g orbitals. These features are also present in the CAM-B3LYP/CIS spectra. Addition of Cp ligands results in strong π donor interactions between the Cp ligand and the metal d xz and d yz orbitals, resulting in the splitting. This is more apparent at the chlorine K-edge due to reduction of Cl(3p) contributions to the Ti(3d) orbitals when Cl is replaced by Cp. With the increase in the number of Cp ligands, the splitting changes. Higher-energy d-orbitals have a more significant contribution from the Cp ligands, hence with an increased number of Cp ligands the intensity of the splitting is reversed. Experimentally, this happens at both the titanium and chlorine K-edges although in the simulated spectra the effect is more prominent at the chlorine K-edge.