Shrinking the Synchrotron: Tabletop Extreme Ultraviolet Absorption of Transition-Metal Complexes

We show that the electronic structure of molecular first-row transition-metal complexes can be reliably measured using tabletop high-harmonic XANES at the metal M_2,3 edge. Extreme ultraviolet photons in the 50-70 eV energy range probe 3p → 3d transitions, with the same selection rules as soft X-ray L_2,3-edge absorption (2p → 3d excitation). Absorption spectra of model complexes are sensitive to the electronic structure of the metal center, and ligand field multiplet simulations match the shapes and peak-to-peak spacings of the experimental spectra. This work establishes high-harmonic spectroscopy as a powerful tool for studying the electronic structure of molecular inorganic, bioinorganic, and organometallic compounds.