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

Autor: Zhang K; Department of Chemistry, University of Illinois at Urbana-Champaign , Champaign 61801, United States., Lin MF; Department of Chemistry, University of Illinois at Urbana-Champaign , Champaign 61801, United States., Ryland ES; Department of Chemistry, University of Illinois at Urbana-Champaign , Champaign 61801, United States., Verkamp MA; Department of Chemistry, University of Illinois at Urbana-Champaign , Champaign 61801, United States., Benke K; Department of Chemistry, University of Illinois at Urbana-Champaign , Champaign 61801, United States., de Groot FM; Department of Chemistry, Utrecht University , 3584 CG Utrecht, The Netherlands., Girolami GS; Department of Chemistry, University of Illinois at Urbana-Champaign , Champaign 61801, United States., Vura-Weis J; Department of Chemistry, University of Illinois at Urbana-Champaign , Champaign 61801, United States.
Jazyk: angličtina
Zdroj: The journal of physical chemistry letters [J Phys Chem Lett] 2016 Sep 01; Vol. 7 (17), pp. 3383-7. Date of Electronic Publication: 2016 Aug 15.
DOI: 10.1021/acs.jpclett.6b01393
Abstrakt: 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 M2,3 edge. Extreme ultraviolet photons in the 50-70 eV energy range probe 3p → 3d transitions, with the same selection rules as soft X-ray L2,3-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.
Databáze: MEDLINE