Adsorption of molecular oxygen on the Ag(111) surface: A combined temperature-programmed desorption and scanning tunneling microscopy study.

The adsorption of O on Ag(111) between 300 and 500 K has been studied with temperature-programmed desorption (TPD) and scanning tunneling microscopy (STM). At the first stage of adsorption, the disordered local oxide phase (commonly looking in STM as an array of black spots) is formed on the surface irrespective of the substrate temperature. The maximum concentration of black spots was found to be ≈0.

Visualization of Electron Paramagnetic Resonance Hyperfine Structure Coupling Pathways.

The close relation between the EPR hyperfine coupling constant and NMR indirect spin-spin coupling constant is well-known. For example, the Karplus-type dependence of hyperfine constants on the dihedral angle, originally proposed for NMR spin-spin coupling, is widely used in pNMR studies. In the present work we propose a new tool for visualization of hyperfine coupling pathways based on our experience with visualization of NMR indirect spin-spin couplings.

Adsorption of O_{2} on Ag(111): Evidence of Local Oxide Formation.

The atomic structure of the disordered phase formed by oxygen on Ag(111) at low coverage is determined by a combination of low-temperature scanning tunneling microscopy and density functional theory. We demonstrate that the previous assignment of the dark objects in STM to chemisorbed oxygen atoms is incorrect and incompatible with trefoil-like structures observed in atomic-resolution images in current work. In our model, each object is an oxidelike ring formed by six oxygen atoms around the vacancy in Ag(111).

Chemical reduction of the elastic properties of zeolites: a comparison of the formation of carbonate species versus dealumination.

The decrease in elastic moduli (Young's, bulk, and shear modulus), the variations in their asymmetries, the Poisson's ratio and the linear compressibility due to carbonate formation in NaX, have been compared to those produced by dealumination of the zeolite HY framework, from the Al-Si-Al fragment positioned in joined 4R rings. All these systems have been considered at the density functional theory (DFT) level using periodic boundary conditions. The representativeness of the models has been checked by comparison of the calculated IR spectra of carbonate and hydrocarbonate species in NaX and of hydroxyl groups in HY with the experimental equivalents.

Computational differentiation of Brønsted acidity induced by alkaline earth or rare earth cations in zeolites.

For bi- and trivalent Me(q+) (Me = metal) cations of alkaline earth (AE) and rare earth (RE) metals, respectively, the formation of the nonacid MeOH((q-1)+) species and acid H-Ozeo group, where Ozeo is the framework atom, from water adsorbed at the multivalent Me(q+)(H2O) cation in cationic form zeolites was checked at both isolated cluster (8R or 6R + 4R) and periodic (the mordenite framework) levels. Both approaches demonstrate qualitative differences for the stability of the dissociated water between the two classes of industrial cationic forms if two Al atoms are closely located. The RE forms split water while the AE ones do not, that can be a basis of different proton transfer in the RE zeolites (thermodynamic control) than in the AE forms (kinetic control).