title: Ti(3+) Aqueous Solution: Hybridization and Electronic Relaxation Probed by State-Dependent Electron Spectroscopy.
abstract: The electronic structure of a Ti(3+) aqueous solution is studied by liquid-jet soft X-ray photoelectron (PE) spectroscopy. Measured valence and Ti 2p core-level binding energies, together with the Ti 2p resonant photoelectron (RPE) spectra and the derived partial electron-yield L-edge X-ray absorption (PEY-XA) spectra, reveal mixing between metal 3d and water orbitals. Specifically, ligand states with metal character are identified through the enhancement of signal intensities in the RPE spectra. An observed satellite 3d peak structure is assigned to several different metal-ligand states. Experimental energies and the delocalized nature of the respective orbitals are supported by ground-state electronic structure calculations. We also show that by choice of the detected Auger-electron-decay channel, from which different PEY-XA spectra are obtained, the experimental sensitivity to the interactions of the metal 3d electrons with the solvent can be varied. The effect of such a state-dependent electronic relaxation on the shape of the PEY-XA spectra is discussed in terms of different degrees of electron delocalization.
authors.affiliation: †Institute of Methods for Material Development, Helmholtz-Zentrum Berlin, Albert-Einstein-Strasse 15, D-12489 Berlin, Germany.
authors.forename: Robert
authors.initials: R
authors.lastname: Seidel
authors.affiliation: †Institute of Methods for Material Development, Helmholtz-Zentrum Berlin, Albert-Einstein-Strasse 15, D-12489 Berlin, Germany.
authors.forename: Kaan
authors.initials: K
authors.lastname: Atak
authors.affiliation: ‡Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-Ku, Kyoto 606-8502, Japan.
authors.forename: Stephan
authors.initials: S
authors.lastname: Thürmer
authors.affiliation: †Institute of Methods for Material Development, Helmholtz-Zentrum Berlin, Albert-Einstein-Strasse 15, D-12489 Berlin, Germany.|§Department of Physics, Freie Universität Berlin, Arnimallee 14, D-14159 Berlin, Germany.
authors.forename: Emad F
authors.initials: EF
authors.lastname: Aziz
authors.affiliation: †Institute of Methods for Material Development, Helmholtz-Zentrum Berlin, Albert-Einstein-Strasse 15, D-12489 Berlin, Germany.
authors.forename: Bernd
authors.initials: B
authors.lastname: Winter