Intrinsic reconstruction of ice-I surfaces.

Understanding the precise atomic structure of ice surfaces is critical for revealing the mechanisms of physical and chemical phenomena at the surfaces, such as ice growth, melting, and chemical reactions. Nevertheless, no conclusive structure has been established. In this study, noncontact atomic force microscopy was used to address the characterization of the atomic structures of ice Ih(0001) and Ic(111) surfaces. The topmost hydrogen atoms are arranged with a short-range (2 × 2) order, independent of the ice thickness and growth substrates used. The electrostatic repulsion between non-hydrogen-bonded water molecules at the surface causes a reduction in the number of the topmost hydrogen atoms together with a distortion of the ideal honeycomb arrangement of water molecules, leading to a short-range-ordered surface reconstruction.

Realization of Spin-dependent Functionality by Covering a Metal Surface with a Single Layer of Molecules.

An interface of molecule and metal has attracted much attention in the research field of nanoelectronics because of their high degree of design freedom. Here, we demonstrate an efficient spin-to-charge current conversion at the metal surface covered by a single layer of molecules. Spin currents are injected into an interface between metal (Cu) and lead(II) phthalocyanine by means of the spin pumping method. An observed voltage signal is caused by the inverse Edelstein effect, i.e., spin-to-charge current conversion at the interface. The conversion coefficient, inverse Edelstein length, is estimated to be 0.40 ± 0.06 nm, comparable with the largest Rashba spin splitting of interfaces with heavy metals. Interestingly, the Edelstein length strongly depends on the thickness of the molecule and takes a maximum value when a single layer of molecules is formed on the Cu surface. Comparative analysis between scanning probe microscopy and first-principles calculations reveal that the formation of interface state with Rashba spin splitting causes the inverse Edelstein effect, whose magnitude is sensitive to the adsorption configuration of the molecules.

Local electronic structure, work function, and line defect dynamics of ultrathin epitaxial ZnO layers on a Ag(1 1 1) surface.

Using combined low-temperature scanning tunneling microscopy and Kelvin probe force microscopy we studied the local electronic structure and work function change of the (0 0 0 1)-oriented epitaxial ZnO layers on a Ag(1 1 1) substrate. Scanning tunneling spectroscopy (STS) revealed that the conduction band minimum monotonically downshifts as the number of the ZnO layers increases up to 4 monolayers (ML). However, it was found by field emission resonance (FER) spectroscopy that the local work function of Ag(1 1 1) slightly decreases for 2 ML thick ZnO but it dramatically changes and drops by about 1.2 eV between 2 and 3 ML, suggesting a structural transformation of the ZnO layer. The spatial variation of the conduction band minimum and the local work function change were visualized at the nanometer scale by mapping the STS and FER intensities. Furthermore, we found that the ZnO layers contained line defects with a few tens of nm long, which can be removed by the injection of a tunneling electron into the conduction band.

Formation of unique trimer of nitric oxide on Cu(111).

We report that NO molecules unexpectedly prefer a trimeric configuration on Cu(111). We used scanning tunneling microscopy (STM) at 6 K, and confirmed that the NO molecule is bonded to the face-centered-cubic hollow site in an upright configuration. The individual NO molecule is imaged as a ring protrusion, which is characteristic of the doubly degenerate 2π(*) orbital. A triangular trimer is thermodynamically more favorable than the monomer and dimer, and its bonding structure was characterized by STM manipulation. This unique behavior of NO on Cu(111) is ascribed to the threefold symmetry of the surface, facilitating effective mixing of the 2π(*) orbitals in a triangular configuration.

Configuration change of NO on Cu(110) as a function of temperature.

The bonding structure of nitric oxide (NO) on Cu(110) is studied by means of scanning tunneling microscopy, reflection absorption infrared spectroscopy, and electron energy loss spectroscopy at 6-160 K. At low temperatures, the NO molecule adsorbs at the short bridge site via the N end in an upright configuration. At around 50 K, this turns into a flat configuration, in which both the N and O atoms interact with the surface. The flat configuration is characterized by the low-frequency N-O stretching mode at 855 cm(-1). The flat-lying NO flips back and forth when the temperature increases to ~80 K, and eventually dissociates at ~160 K. We propose a potential energy diagram for the conversion of NO on the surface.

H-atom relay reactions in real space.

Hydrogen bonds are the path through which protons and hydrogen atoms can be transferred between molecules. The relay mechanism, in which H-atom transfer occurs in a sequential fashion along hydrogen bonds, plays an essential role in many functional compounds. Here we use the scanning tunnelling microscope to construct and operate a test-bed for real-space observation of H-atom relay reactions at a single-molecule level. We demonstrate that the transfer of H-atoms along hydrogen-bonded chains assembled on a Cu(110) surface is controllable and reversible, and is triggered by excitation of molecular vibrations induced by inelastic tunnelling electrons. The experimental findings are rationalized by ab initio calculations for adsorption geometry, active vibrational modes and reaction pathway, to reach a detailed microscopic picture of the elementary processes.

Imaging covalent bonding between two NO molecules on Cu(110).

Using a scanning tunneling microscope, we found metastable upright NO on Cu(110) with the 2π* molecular resonance at the Fermi level. Upon heating above 40 K, it converts to a bent structure with the loss of molecular resonance. By manipulating the distance between two upright NO, we controlled the overlap between 2π* orbitals and observed its splitting below and above the Fermi level, thus visualizing the covalent interaction between them.

Imaging sequential dehydrogenation of methanol on Cu(110) with a scanning tunneling microscope.

Adsorption of methanol and its dehydrogenation on Cu(110) were studied by using a scanning tunneling microscope (STM). Upon adsorption at 12 K, methanol preferentially forms clusters on the surface. The STM could induce dehydrogenation of methanol sequentially to methoxy and formaldehyde. This enabled us to study the binding structures of these products in a single-molecule limit. Methoxy was imaged as a pair of protrusion and depression along the [001] direction. This feature is fully consistent with the previous result that it adsorbs on the short-bridge site with the C-O axis tilted along the [001] direction. The axis was induced to flip back and forth by vibrational excitations with the STM. Two configurations were observed for formaldehyde, whose structures were proposed based on their characteristic images and motions.