Ti3 Aqueous Solution Hybridization and Electronic Relaxation Probed by State Dependent Electron Spectroscopy

Abstract

The electronic structure of a Ti3 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 delocalizatio