Ultrafast X-ray absorption spectroscopy is a powerful tool to observe electronic and geometric structures of short-lived reaction intermediates. The ab initio FEFF9 code is applied to simulate the Pt L-3-edge XANES spectrum of the photocatalytic diplatinum molecule Pt-2(P2O5H2)(4) and the photo-induced changes that occur therein. The spectra are interpreted within a XAFS-like scattering theoretical framework (bound-continuum transitions) or in terms of a final-state local l-projected density of states (LDOS) (bound-bound transitions). By using a novel Bayesian fitting procedure, we show that the ground-state structures obtained independently from the XANES and EXAFS regions of the spectrum are in good agreement with each other. The semi-quantitative result obtained for the Pt-Pt contraction in the excited state is in line with recently published values. The improved theoretical treatment of inelastic losses has shown to result in more accurate peak positions in the above-continuum region of the spectrum which is an important prerequisite for obtaining quantitative structural information from (time-resolved) XANES spectra.