115 research outputs found
Oxygen vacancies as active sites for water dissociation on rutile TiO<sub>2</sub>(110)
Through an interplay between scanning tunneling microscopy experiments and density functional theory calculations, we determine unambiguously the active surface site responsible for the dissociation of water molecules adsorbed on rutile TiO2(110). Oxygen vacancies in the surface layer are shown to dissociate H2O through the transfer of one proton to a nearby oxygen atom, forming two hydroxyl groups for every vacancy. The amount of water dissociation is limited by the density of oxygen vacancies present on the clean surface exclusively. The dissociation process sets in as soon as molecular water is able to diffuse to the active site
Palladium Nanocrystals on Al<sub>2</sub>O<sub>3</sub>: Structure and Adhesion Energy
We have investigated the structure and morphology of nanosized palladium clusters supported by a thin Al2O3 film on NiAl(110) using scanning tunneling microscopy. Well-ordered clusters with a diameter above ≈40Å were imaged with atomic resolution, allowing a crystallographic identification of the cluster facets. A new method to obtain quantitative information on the work of adhesion (adhesion energy) of metal clusters deposited on oxides is introduced. For Pd on Al2O3 we obtain a value of Wadh=2.8±0.2J/m2. This result is at variance with values recently derived on the basis of ab initio density-functional theory
Bonding of gold nanoclusters to oxygen vacancies on rutile TiO2(110)
Through an interplay between scanning tunneling microscopy (STM) and density functional theory (DFT) calculations, we show that bridging oxygen vacancies are the active nucleation sites for Au clusters on the rutile TiO2(110) surface. We find that a direct correlation exists between a decrease in density of vacancies and the amount of Au deposited. From the DFT calculations we find that the oxygen vacancy is indeed the strongest Au binding site. We show both experimentally and theoretically that a single oxygen vacancy can bind 3 Au atoms on average. In view of the presented results, a new growth model for the TiO2(110) system involving vacancy-cluster complex diffusion is presented
Band Calculation for Ce-compounds on the basis of Dynamical Mean Field Theory
The band calculation scheme for electron compounds is developed on the
basis of the dynamical mean field theory (DMFT) and the LMTO method. The
auxiliary impurity problem is solved by a method named as NCAv', which
includes the correct exchange process of the virtual
excitation as the vertex correction to the non-crossing approximation (NCA) for
the fluctuation. This method leads to the correct magnitude
of the Kondo temperature, , and makes it possible to carry out
quantitative DMFT calculation including the crystalline field (CF) and the
spin-orbit (SO) splitting of the self-energy. The magnetic excitation spectra
are also calculated to estimate . It is applied to Ce metal and CeSb
at T=300 K as the first step. In Ce metal, the hybridization intensity (HI)
just below the Fermi energy is reduced in the DMFT band. The photo-emission
spectra (PES) have a conspicuous SO side peak, similar to that of experiments.
is estimated to be about 70 K in -Ce, while to be about
1700 K in -Ce. In CeSb, the double-peak-like structure of PES is
reproduced. In addition, which is not so low is obtained because HI
is enhanced just at the Fermi energy in the DMFT band.Comment: 30pages, 18 figure
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