Seidel Robert, Atak Kaan, Thürmer Stephan, Aziz Emad F, Winter Bernd
†Institute of Methods for Material Development, Helmholtz-Zentrum Berlin, Albert-Einstein-Strasse 15, D-12489 Berlin, Germany.
‡Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-Ku, Kyoto 606-8502, Japan.
J Phys Chem B. 2015 Aug 20;119(33):10607-15. doi: 10.1021/acs.jpcb.5b03337. Epub 2015 Aug 6.
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.
通过液滴软X射线光电子能谱对Ti(3+)水溶液的电子结构进行了研究。测量得到的价态和Ti 2p芯能级结合能，以及Ti 2p共振光电子能谱（RPE）和推导得到的部分电子产额L边X射线吸收能谱（PEY-XA），揭示了金属3d轨道和水轨道之间的混合。具体而言，通过RPE能谱中信号强度的增强确定了具有金属特性的配体态。观察到的卫星3d峰结构被归因于几种不同的金属-配体态。基态电子结构计算支持了实验得到的能量以及各个轨道的离域性质。我们还表明，通过选择检测俄歇电子衰变通道（从中可获得不同的PEY-XA能谱），可以改变实验对金属3d电子与溶剂相互作用的灵敏度。根据不同程度 的电子离域讨论了这种状态依赖的电子弛豫对PEY-XA能谱形状的影响。
