TiO2 anatase plays a central role in energy and environmental research. A major bottleneck toward developing artificial photosynthesis with TiO2 is that it only absorbs ultraviolet light, owing to its large bandgap of 3.2 eV. If one could reduce the bandgap of anatase to the visible region, TiO2-based photocatalysis could become a competitive clean energy source. Here, using scanning tunneling microscopy and spectroscopy in conjunction with density functional theory calculations, we report the discovery of a highly reactive titanium-terminated anatase surface with a reduced bandgap of less than 2 eV, stretching into the red portion of the solar spectrum. By tuning the surface preparation conditions, we can reversibly switch between the standard anatase surface and the newly discovered low bandgap surface phase. The identification of a TiO2 anatase surface phase with a bandgap in the visible and high chemical reactivity has important implications for solar energy conversion, photocatalysis, and artificial photosynthesis.

Dye-sensitized solar cells constitute a promising approach to sustainable and low-cost solar energy conversion. Their overall efficiency crucially depends on the effective coupling of the photosensitizers to the photoelectrode and the details of the dye's energy levels at the interface. Despite great efforts, the specific binding of prototypical ruthenium-based dyes to TiO2, their potential supramolecular interaction, and the interrelation between adsorption geometry and electron injection efficiency lack experimental evidence. Here we demonstrate multiconformational adsorption and energy level alignment of single N3 dyes on TiO2 anatase (101) revealed by scanning tunnelling microscopy and spectroscopy. The distinctly bound molecules show significant variations of their excited state levels associated with different driving forces for photoelectron injection. These findings emphasize the critical role of the interfacial coupling and suggest that further designs of dye-sensitized solar cells should target a higher selectivity in the dye-substrate binding conformations in order to ensure efficient electron injection from all photosensitizers.

The adsorption of pyrimidine onto Ge(100) surfaces has been investigated using real-time scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), and density-functional theory (DFT) calculations. Our results show that the adsorbed pyrimidine molecules are tilted about 40 degrees with respect to the Ge surface, and through a Lewis acid-base reaction form bridges between the down-Ge atoms of neighboring Ge dimer rows by double Ge-N dative bonding without loss of aromaticity. For coverages of pyrimidine up to 0.25 ML, a well-ordered c(4x2) structure results from states that appear in STM micrographs as oval-shaped protrusions, which correspond to pyrimidine molecules datively adsorbed on every other dimer. However, above 0.25 ML, the oval-shaped protrusions gradually change into brighter zigzag lines. At 0.50 ML, a p(2x2) structure results from the states that appear in STM as zigzag lines. The zigzag lines are formed by the attachment of pyrimidine molecules to the down-Ge atoms of every Ge dimer. However, the unstable p(2x2) structure eventually reconstructs into a c(4x2) structure due to steric hindrance between the adsorbed pyrimidine molecules after stopping the exposure of pyrimidine to the surface.

The adsorption structure of glycine on Ge(100) was investigated using scanning tunneling microscopy (STM), density functional theory (DFT) calculations, and high-resolution core-level photoemission spectroscopy (HRCLPES). We found a major adsorption feature of glycine on Ge(100) in the STM images. This feature appeared as a bright protrusion between two dimer rows with a dark adjacent dimer. The position of the bright protrusion located in the middle of the two dimer rows indicates a multibonding adsorption structure. The results of the theoretical calculations confirm that the adsorption structure of glycine on Ge(100) (between two possible multibonding adsorption structures) is an "intrarow O-H dissociated and N dative bonded structure". In the HRCLPES experiments, we found an N 1s peak (at 399.5 eV) and two O 1s peaks (at 531.1 and 532.0 eV), which represent strong evidence that the adsorption configuration of glycine on Ge(100) is composed of both O-H dissociation and N dative bonding. All our STM, DFT, and HRCLPES results suggest that the adsorption structure of glycine molecules on Ge(100) is an "intrarow O-H dissociated and N dative bonded structure".