We address the adsorption of water on Pt(111) using x-ray absorption, x-ray emission, and x-ray photoelectron spectroscopy along with calculations in the framework of density functional theory. Using the direct relationship between the electronic structure and adsorbate geometry, we show that in the first layer all the molecules bind directly to the surface and to each other through the in-layer H bonds without dissociation, creating a nearly flat overlayer. The water molecules are adsorbed through alternating metal-oxygen (M-O) and metal-hydrogen (M-HO) bonds.

A joint experimental and theoretical work to explain the electronic and geometrical structure of an in situ prepared film of iron phthalocyanine (FePc) on silicon (100) is presented. FePc molecular films have been characterized by core and valence photoemission spectroscopy (PES) and x-ray absorption spectroscopy (XAS), and the results have been interpreted and simulated by density functional theory (DFT) calculations. C1s and N1s PE spectra have been analyzed by taking into account all chemically nonequivalent C and N atoms in the molecule. In the Fe2p(32) spectra it has been possible to resolve two components that can be related to the open shell structure of the molecule. By valence PES and N1s XAS data, the geometrical orientation of the FePc molecules in the film could be determined. Our results indicate that for the FePc on Si(100), the molecules within the film are mainly standing on the surface. The experimental N1s XAS spectra are very well reproduced by the theoretical calculations, which are both angle and atomic resolved, giving a detailed description of the electronic and geometric structure of the FePc film. Furthermore, the asymmetry and the intensity angle variation of the first N1s XAS threshold feature could be explained by the presented DFT calculations as due to the chemical nonequivalence of the N atoms and the symmetry character of the lowest unoccupied molecular orbital.

For the electrochemical hydrogen evolution reaction (HER), the electrical properties of catalysts can play an important role in influencing the overall catalytic activity. This is particularly important for semiconducting HER catalysts such as MoS , which has been extensively studied over the last decade. Herein, on-chip microreactors on two model catalysts, semiconducting MoS and semimetallic WTe , are employed to extract the effects of individual factors and study their relations with the HER catalytic activity. It is shown that electron injection at the catalyst/current collector interface and intralayer and interlayer charge transport within the catalyst can be more important than thermodynamic energy considerations. For WTe , the site-dependent activities and the relations of the pure thermodynamics to the overall activity are measured and established, as the microreactors allow precise measurements of the type and area of the catalytic sites. The approach presents opportunities to study electrochemical reactions systematically to help establish rational design principles for future electrocatalysts.

The electronic structure of a vapor-sublimated thin film of metal-free phthalocyanine (H2Pc) is studied experimentally and theoretically. An atom-specific picture of the occupied and unoccupied electronic states is obtained using x-ray-absorption spectroscopy (XAS), core- and valence-level x-ray photoelectron spectroscopy (XPS), and density-functional theory (DFT) calculations. The DFT calculations allow for an identification of the contributions from individual nitrogen atoms to the experimental N1s XAS and valence XPS spectra. This comprehensive study of metal-free phthalocyanine is relevant for the application of such molecules in molecular electronics and provides a solid foundation for identifying modifications in the electronic structure induced by various substituent groups.