Ab initio studies of hydrogen desorption from low index magnesium hydride surface

The low index Magnesium hydride surfaces, MgH2(001) and MgH2(110), have been studied by ab intio Density Functional Theory (DFT) calculations. It was found that the MgH2(110) surface is more stable than MgH2(001) surface, which is in good agreement with the experimental observation. The H-2 desorption barriers vary depending on the crystalline surfaces that are exposed and also the specific H atom sites involved-they are found to be generally high, due to the thermodynamic stability of the MgH2, system, and are larger for the MgH2(001) surface. The pathway for recombinative desorption of one in-plane and one bridging H atom from the MgH2(110) surface was found to be the lowest energy barrier amongst those computed (172 KJ/mol) and is in good agreement with the experimental estimates. (c) 2006 Elsevier B.V. All rights reserved.

Propriedades eletrônicas e estruturais do PbTiO3: teoria do funcional de densidade aplicada a modelos periódicos

Calculations based on density functional theory at the B3LYP hybrid functional level applied to periodic models have been performed to characterize the structural and electronic properties of PbTiO3. Two different slab terminations (PbO and TiO2) have been considered to obtain and discuss the results of band structure, density of states, charge distribution on bulk and surface relaxation. It is observed that the relaxation processes are most prominent for the Ti and Pb surface atoms. The electron density maps confirm the partial covalent character of the Ti-O bonds. The calculated optical band gap and other results are in agreement with experimental data.

Epitaxial growth of ultrathin palladium films on Re{0001}

Ultrathin bimetallic layers create unusual magnetic and surface chemical effects through the modification of electronic structure brought on by low dimensionality, polymorphism, reduced screening, and epitaxial strain. Previous studies have related valence and core-level shifts to surface reactivity through the d-band model of Hammer and Nørskov, and in heteroepitaxial films this band position is determined by competing effects of coordination, strain, and hybridization of substrate and overlayer states. In this study we employ the epitaxially matched Pd on Re{0001} system to grow films with no lateral strain. We use a recent advancement in low-energy electron diffraction to expand the data range sufficiently for a reliable determination of the growth sequence and out-of-plane surface relaxation as a function of film thickness. The results are supported by scanning tunneling microscopy and X-ray photoemission spectroscopy, which show that the growth is layer-by-layer with significant core-level shifts due to changes in film structure, morphology, and bonding.

Periodic study on the structural and electronic properties of bulk, oxidized and reduced SnO2(110) surfaces and the interaction with O-2

The structural and electronic properties of bulk and both oxidized and reduced SnO2(110) surfaces as well as the adsorption process of O-2 on the reduced surface have been investigated by periodic DFT calculations at B3LYP level. The lattice parameters, charge distribution, density of states and band structure are reported for the bulk and surfaces. Surface relaxation effects have been explicitly taken into account by optimizing slab models of nine and seven atomic layers representing the oxidized and reduced surfaces, respectively. The conductivity behavior of the reduced SnO2(110) surface is explained by a distribution of the electrons in the electronic states in the band gap induced by oxygen vacancies. Three types of adsorption approaches of O-2 on the four-fold tin at the reduced SuO(2)(110) surface have been considered. The most exothermic channel corresponds to the adsorption of O-2 parallel to the surface and to the four-fold tin row, and it is believed to be associated with the formation of a peroxo O-2(2-) species. The chemisorption of O-2 on reduced SnO2(110) surface causes a significant depopulation of states along the band gap and it is shown to trap the electrons in the chemisorbed complex producing an electron-depleted space-charge layer in the inner surface region of the material in agreement with some experimental evidences. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Propriedades eletrônicas e estruturais do PbTiO3: teoria do funcional de densidade aplicada a modelos periódicos

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Local electromethanical properties of the CaCu 3Ti 4O 12 ceramics

Scanning probe microscopy (SPM) was used to probe piezoelectric vibrations and local conductivity in CaCu 3Ti 4O 12 (CCTO) ceramics at room temperature. Piezoelectric contrast was observed on the polished surfaces of CCTO in both vertical (out-of-plane) and lateral (in-plane) modes and depended on the grain orientation varying in sign and amplitude. The piezoelectric contrast is shown to be controlled by the electrical bias (local poling) and displayed a ferroelectric-like reversible hysteresis accompanied with a change of the phase of piezoelectric signal. Flexoelectric effect (strain-gradient-induced polarization) due to surface relaxation was invoked to explain the observed contrast inside the grains. © 2010 Materials Research Society.

From In Situ towards In Operando Conditions: Scanning Tunneling Microscopy Study of Hydrogen Intercalation in Cu(111) during Hydrogen Evolution

We used electrochemical scanning tunneling microscopy to study the intercalation of hydrogen into a Cu(111) model electrode under reactive (in operando) conditions. Hydrogen evolution causes hydrogen intermediates to migrate into the copper lattice as function of the applied potential and the resulting current density. This H-inclusion is demonstrated to be reversible. The presence of subsurface hydrogen leads to a significant surface relaxation/reconstruction affecting both the geometric and electronic structure of the electrode surface.

Relaxation of surface tension in the free-surface boundary layers of simple Lennard-Jones liquids

In this paper we use molecular dynamics to answer a classical question: how does the surface tension on a liquid/gas interface appear? After defining surface tension from the first principles and performing several consistency checks, we perform a dynamic experiment with a single simple liquid nanodroplet. At time zero, we remove all molecules of the interfacial layer of molecules, creating a fresh bare interface with the bulk arrangement of molecules. After that the system evolves towards equilibrium, and the expected surface tension is re-established. We found that the system relaxation consists of three distinct stages. First, the mechanical balance is quickly re-established. During this process the notion of surface tension is meaningless. In the second stage, the surface tension equilibrates, and the density profile broadens to a value which we call “intrinsic” interfacial width. During the third stage, the density profile continues to broaden due to capillary wave excitations, which does not however affect the surface tension.We have observed this scenario for monatomic Lennard-Jones (LJ) liquid as well as for binary LJ mixtures at different temperatures, monitoring a wide range of physical observables.

Relaxation of surface tension in the liquid-solid interfaces of Lennard-Jones liquids

We have established the surface tension relaxation time in the liquid-solid interfaces of Lennard-Jones (LJ) liquids by means of direct measurements in molecular dynamics (MD) simulations. The main result is that the relaxation time is found to be almost independent of the molecular structures and viscosity of the liquids (at seventy-fold change) used in our study and lies in such a range that in slow hydrodynamic motion the interfaces are expected to be at equilibrium. The implications of our results for the modelling of dynamic wetting processes and interpretation of dynamic contact angle data are discussed.

The role of an insulating surface layer on the relaxation time of the ionic redistribution in an electrolytic cell

We analyze the influence of a surface dielectric layer on the transient phenomena related to the ionic redistribution in an electrolytic cell submitted to a step-like external voltage. The adsorption-desorption phenomenon is taken into account in the famework of the Gouy-Chapman approximation, where the ions are assumed dimensionless. In the limit of small amplitude of the applied voltage, where the equations of the problem can be linearized, we obtain an analytical solution for the surface densities of ions, for the electrical potential and for the relaxation time for the transient phenomena. In the general case, when the linearized analysis is no longer valid, the solution of the problem is obtained numerically. The role of the thickness of the dielectric layer on the relaxation time is also discussed.

Evidence for energy relaxation via a radiative cascade in surface-passivated PbS quantum dots

Multiple emission peaks have been observed from surface passivated PbS nanocrystals displaying strong quantum confinement. The emission spectra are shown to be strongly dependent on the excited-state parity. We also find that intraband energy relaxation from initial states excited far above the band-edge is nearly three orders of magnitude slower than that found in other nanocrystal quantum dots, providing evidence of inefficient energy relaxation via phonon emission. The initial-state parity dependence of the photoluminescent emission properties suggests that energy relaxation from the higher excited states occurs via a radiative cascade, analogous to energy relaxation in atomic systems. Such radiative cascade emission is possible from ideal zero-dimensional semiconductors, where electronic transitions can be decoupled from phonon modes.

Inorganic surface passivation of PbS nanocrystals resulting in strong photoluminescent emission

Strong photoluminescent emission has been obtained from 3 nm PbS nanocrystals in aqueous colloidal solution, following treatment with CdS precursors. The observed emission can extend across the entire visible spectrum and usually includes a peak near 1.95 eV. We show that much of the visible emission results from absorption by higher-lying excited states above 3.0 eV with subsequent relaxation to and emission from states lying above the observed band-edge of the PbS nanocrystals. The fluorescent lifetimes for this emission are in the nanosecond regime, characteristic of exciton recombination.

Surface foam film waves studied with high-speed linescan camera

Dynamic foam films have been investigated using an improved experimental set-up with a CCD high-speed linescan camera in conjunction with the Scheludko micro-interferometric cell for studying the drainage and rupture of liquid foam films. The improved experimental set-up increased the sensibility of detection of the local thickness heterogeneities and domains during the film evolution. The evolution of the foam films up to the formation of black spots was recorded in the time intervals of 50ms. The wavelengths of the propagating surface waves and their frequencies were determined experimentally. The experimental results show that the current quasi-static hydrodynamic theory does not properly describe the wave dynamics with inter-domain channels. However, the thermodynamic condition for formation of black spots in the foam films was met by the experimental results. (c) 2005 Elsevier B.V. All rights reserved.

The effect of counterpoise correction and relaxation energy term to the internal rotation barriers: application to the BF3 ...NH3 and C2H4 ...SO2 dimers

The relevance of the fragment relaxation energy term and the effect of the basis set superposition error on the geometry of the BF3⋯NH3 and C2H4⋯SO2 van der Waals dimers have been analyzed. Second-order Møller-Plesset perturbation theory calculations with the d95(d,p) basis set have been used to calculate the counterpoise-corrected barrier height for the internal rotations. These barriers have been obtained by relocating the stationary points on the counterpoise-corrected potential energy surface of the processes involved. The fragment relaxation energy can have a large influence on both the intermolecular parameters and barrier height. The counterpoise correction has proved to be important for these systems