Time-dependent density functional theory (TDDFT) coupled to the relativistic two-component zeroth-order regular approximation, both available in the last version of the ADF package, have been successfully used to simulate X-ray absorption spectra of TiCl4, Ti(eta(5)-C5H5)Cl-3, and Ti(eta(5)-C5H5)(2)Cl-2 in terms of their oscillator strength distributions. Besides allowing a first principle assignment of Ti 1s, Cl 1s, and Ti 2p (L-2,L-3 edges) core excitation spectra, theoretical outcomes provide a rationale for deviations from the expected L-3/L-2 branching ratio.