Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters

The knowledge of the atomic structure of clusters composed by few atoms is a basic prerequisite to obtain insights into the mechanisms that determine their chemical and physical properties as a function of diameter, shape, surface termination, as well as to understand the mechanism of bulk formation. Due to the wide use of metal systems in our modern life, the accurate determination of the properties of 3d, 4d, and 5d metal clusters poses a huge problem for nanoscience. In this work, we report a density functional theory study of the atomic structure, binding energies, effective coordination numbers, average bond lengths, and magnetic properties of the 3d, 4d, and 5d metal (30 elements) clusters containing 13 atoms, M(13). First, a set of lowest-energy local minimum structures (as supported by vibrational analysis) were obtained by combining high-temperature first- principles molecular-dynamics simulation, structure crossover, and the selection of five well-known M(13) structures. Several new lower energy configurations were identified, e. g., Pd(13), W(13), Pt(13), etc., and previous known structures were confirmed by our calculations. Furthermore, the following trends were identified: (i) compact icosahedral-like forms at the beginning of each metal series, more opened structures such as hexagonal bilayerlike and double simple-cubic layers at the middle of each metal series, and structures with an increasing effective coordination number occur for large d states occupation. (ii) For Au(13), we found that spin-orbit coupling favors the three-dimensional (3D) structures, i.e., a 3D structure is about 0.10 eV lower in energy than the lowest energy known two-dimensional configuration. (iii) The magnetic exchange interactions play an important role for particular systems such as Fe, Cr, and Mn. (iv) The analysis of the binding energy and average bond lengths show a paraboliclike shape as a function of the occupation of the d states and hence, most of the properties can be explained by the chemistry picture of occupation of the bonding and antibonding states.

Density functional theory and ab initio molecular dynamics study of NO adsorption on Pd(111) and Pt(111) surfaces

The origin of the unique geometry for nitric oxide (NO) adsorption on Pd(111) and Pt(111) surfaces as well as the effect of temperature were studied by density functional theory calculations and ab initio molecular dynamics at finite temperature. We found that at low coverage, the adsorption geometry is determined by electronic interactions, depending sensitively on the adsorption sites and coverages, and the effect of temperature on geometries is significant. At coverage of 0.25 monolayer (ML), adsorbed NO at hollow sites prefer an upright configuration, while NO adsorbed at top sites prefer a tilting configuration. With increase in the coverage up to 0.50 ML, the enhanced steric repulsion lead to the tilting of hollow NO. We found that the tilting was enhanced by the thermal effects. At coverage of 0.75 ML with p(2 x 2)-3NO(fcc+hcp+top) structure, we found that there was no preferential orientation for tilted top NO. The interplay of the orbital hybridization, thermal effects, steric repulsion, and their effects on the adsorption geometries were highlighted at the end.

Structure, stability, depolarized light scattering, and vibrational spectra of fullerenols from all-electron density-functional-theory calculations

We have investigated the stability, electronic properties, Rayleigh (elastic), and Raman (inelastic) depolarization ratios, infrared and Raman absorption vibrational spectra of fullerenols [C(60)(OH)(n)] with different degrees of hydroxylation by using all-electron density-functional-theory (DFT) methods. Stable arrangements of these molecules were found by means of full geometry optimizations using Becke's three-parameter exchange functional with the Lee, Yang, and Parr correlation functional. This DFT level has been combined with the 6-31G(d,p) Gaussian-type basis set, as a compromise between accuracy and capability to treat highly hydroxylated fullerenes, e.g., C(60)(OH)(36). Thus, the molecular properties of fullerenols were systematically analyzed for structures with n=1, 2, 3, 4, 8, 10, 16, 18, 24, 32, and 36. From the electronic structure analysis of these molecules, we have evidenced an important effect related to the weak chemical reactivity of a possible C(60)(OH)(24) isomer. To investigate Raman scattering and the vibrational spectra of the different fullerenols, frequency calculations are carried out within the harmonic approximation. In this case a systematic study is only performed for n=1-4, 8, 10, 16, 18, and 24. Our results give good agreements with the expected changes in the spectral absorptions due to the hydroxylation of fullerenes.

Excitation energies from ground-state density-functionals by means of generator coordinates

The generator-coordinate method is a flexible and powerful reformulation of the variational principle. Here we show that by introducing a generator coordinate in the Kohn-Sham equation of density-functional theory, excitation energies can be obtained from ground-state density functionals. As a viability test, the method is applied to ground-state energies and various types of excited-state energies of atoms and ions from the He and the Li isoelectronic series. Results are compared to a variety of alternative DFT-based approaches to excited states, in particular time-dependent density-functional theory with exact and approximate potentials.

Bulk structures of PtO and PtO(2) from density functional calculations

Platinum plays an important role in catalysis and electrochemistry, and it is known that the direct interaction of oxygen with Pt surfaces can lead to the formation of platinum oxides (PtO(x)), which can affect the reactivity. To contribute to the atomistic understanding of the atomic structure of PtO(x), we report a density functional theory study of the atomic structure of bulk PtO(x) (1 <= x <= 2). From our calculations, we identified a lowest-energy structure (GeS type, space group Pnma) for PtO, which is 0.181 eV lower in energy than the structure suggested by W. J. Moore and L. Pauling [J. Am. Chem. Soc. 63, 1392 (1941)] (PtS type). Furthermore, two atomic structures were identified for PtO(2), which are almost degenerate in energy with the lowest-energy structure reported so far for PtO(2) (CaCl(2) type). Based on our results and analysis, we suggest that Pt and O atoms tend to form octahedron motifs in PtO(x) even at lower O composition by the formation of Pt-Pt bonds.

Near infrared spectroscopy for soil bulk density assessment

P>Soil bulk density values are needed to convert organic carbon content to mass of organic carbon per unit area. However, field sampling and measurement of soil bulk density are labour-intensive, costly and tedious. Near-infrared reflectance spectroscopy (NIRS) is a physically non-destructive, rapid, reproducible and low-cost method that characterizes materials according to their reflectance in the near-infrared spectral region. The aim of this paper was to investigate the ability of NIRS to predict soil bulk density and to compare its performance with published pedotransfer functions. The study was carried out on a dataset of 1184 soil samples originating from a reforestation area in the Brazilian Amazon basin, and conventional soil bulk density values were obtained with metallic ""core cylinders"". The results indicate that the modified partial least squares regression used on spectral data is an alternative method for soil bulk density predictions to the published pedotransfer functions tested in this study. The NIRS method presented the closest-to-zero accuracy error (-0.002 g cm-3) and the lowest prediction error (0.13 g cm-3) and the coefficient of variation of the validation sets ranged from 8.1 to 8.9% of the mean reference values. Nevertheless, further research is required to assess the limits and specificities of the NIRS method, but it may have advantages for soil bulk density predictions, especially in environments such as the Amazon forest.

Intra and interannual variability in the Madeira River water chemistry and sediment load

Concentrations of cations (Na(+), Ca(2+), Mg(2+), K(+), NH(4) (+)), anions (HCO(3) (-), Cl(-), NO(3) (-), SO(4) (2-), PO(4) (3-)) and suspended sediments in the Madeira River water were determined near the city of Porto Velho (RO), in order to assess variation in water chemistry from 2004 to 2007. Calcium and bicarbonate were the dominant cation and anion, respectively. Significant seasonal differences were found, with highest concentrations occurring during the dry season, as expected from the drainage of Andean carbonate-rich substratum. Interannual variations were also observed, but became significant only when annual average discharge was 25% less than normal. Under this atypical discharge condition, bicarbonate was replaced by sulfate, and higher suspended sediment concentrations and loads were also observed. Compared to previously published studies, it appears that no significant changes in water chemistry have occurred during the last 20-30 years, although differences in approaches and sampling designs among this and previous studies may not allow detection of modest changes. The calculated suspended sediment load reported here is close to the values presented elsewhere, reinforcing the relative importance of this river as a sediment supplier for the Amazon Basin. Seasonality has a significant control on the chemistry of Madeira River waters, and severe decrease in discharge due to anthropogenic changes, such as construction of reservoirs or the occurrence of drier years-a plausible consequence of global climate change-may lead to modification in the chemical composition as well in the sediment deliver to the Amazon River.

Change in central kinin B2 receptor density after exercise training in rats

Cardiovascular responses elicited by the stimulation of kinin B2 receptors in the IV cerebral ventricle paratrigeminal nucleus or in the thoracic spinal cord are similar to those observed during an exercise bout Considering that the kalikrein-kinin system (KKS) could act on the cardiovascular modulation during behavioral responses as physical exercise or stress this study evaluated the central B2 receptor densities of Wistar (W) and spontani ously hypertensive rats (SHR) after chronic moderate exercise Animals we re exercise-trained for ten weeks on a treadmill Afterwards systolic blood pressure decreased in both trained strains Animals were killed and the medulla and spinal cord extracted for B2 receptor autoradiography Trained animals were compared to their sedentary controls Sedentary groups showed specific binding sites for Hoe-140 (fmol/mg of tissue) in laminas 1 and 2 of the spinal cord nucleus of the solitary tract (NTS) area postrema (AP) spinal trigeminal tract (sp5) and paratrigeminal nucleus (Pa5) In trained W a significant increase (p<0 05) in specific binding was observed in the Pa5 (31 3%) and NTS (28 2%) Trained SHR showed a significant decrease in n ceptor density in lamina 2 (21 9%) of the thoracic spinal cord and an increase in specific binding in Pa5 (36 1%) We suggest that in the medulla chronic exercise could hyper stimulate the KKS enhancing their efficiency through the increase of B2 receptor density involving this receptor in central cardiovascular control during exercise or stress In the lamina 2 B2 receptor might be involved in the exercise-induced hypotension (C) 2010 Elsevier BV All rights reserved

Methods of quantification of training load in exercise performed at maximal lactate steady state

The aim of the present study was to compare and correlate training impulse (TRIMP) estimates proposed by Banister (TRIMP(Banister)), Stagno (TRIMP(Stagno)) and Manzi (TRIMP(Manzi)). The subjects were submitted to an incremental test on cycle ergometer with heart rate and blood lactate concentration measurements. In the second occasion, they performed 30 min. of exercise at the intensity corresponding to maximal lactate steady state, and TRIMP(Banister), TRIMP(Stagno) and TRIMP(Manzi) were calculated. The mean values of TRIMP(Banister) (56.5 +/- 8.2 u.a.) and TRIMP(Stagno) (51.2 +/- 12.4 u.a.) were not different (P > 0.05) and were highly correlated (r = 0.90). Besides this, they presented a good agreement level, which means low bias and relatively narrow limits of agreement. On the other hand, despite highly correlated (r = 0.93), TRIMP(Stagno) and TRIMP(Manzi) (73.4 +/- 17.6 u.a.) were different (P < 0.05), with low agreement level. The TRIMP(Banister) e TRIMP(Manzi) estimates were not different (P = 0.06) and were highly correlated (r = 0.82), but showed low agreement level. Thus, we concluded that the investigated TRIMP methods are not equivalent. In practical terms, it seems prudent monitor the training process assuming only one of the estimates.

The influence of microstructure on the maximum load and fracture energy of refractory castables

Refractory castables are composed of fractions of fine to fairly coarse particles. The fine fraction is constituted primarily of raw materials and calcium aluminate cement, which becomes hydrated, forming chemical bonds that stiffen the concrete during the curing process. The present study focused on an evaluation of several characteristics of two refractory castables with similar chemical compositions but containing aggregates of different sizes. The features evaluated were the maximum load, the fracture energy, and the ""relative crack-propagation work"" of the two castables heat-treated at 110, 650, 1100 and 1550 degrees C. The results enabled us to draw the following conclusions: the heat treatment temperature exerts a significant influence on the matrix/aggregate interaction, different microstructures form in the castables with temperature, and a relationship was noted between the maximum load and the fracture energy. (C) 2009 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Tropical woods: influence of density in hardness parallel and normal to the grain for some Brazilian tropical tree species

The aim of this work is to verify the possibility to correlating specific gravity and wood hardness parallel and perpendicular to the grain. The purpose is to offer one more tool to help in the decision about wood species choice for use in floors and sleepers. To reach this intent, we considered the results of standard tests (NBR 7190:1997, Timber Structures Design, Annex B, Brazilian Association of Technical Standards) to determine hardness parallel and normal to the grain in fourteen tropical high density wood species (over 850 kg/m(3), at 12% moisture content). For each species twelve determinations were made, based on the material obtained at Sao Carlos and its regional wood market. Statistical analysis led to some expressions to describe the cited properties relationships, with a determination coefficient about 0.8.

Influence of physical and geometrical parameters on three-dimensional load transfer mechanism at tunnel face

Three-dimensional discretizations used in numerical analyses of tunnel construction normally include excavation step lengths much shorter than tunnel cross-section dimensions. Simulations have usually worked around this problem by using excavation steps that are much larger than the actual physical steps used in a real tunnel excavation. In contrast, the analyses performed in this study were based on finely discretized meshes capable of reproducing the excavation lengths actually used in tunnels, and the results obtained for internal forces are up to 100% greater than those found in other analyses available in the literature. Whereas most reports conclude that internal forces depend on support delay length alone, this study shows that geometric path dependency (reflected by excavation round length) is very strong, even considering linear elasticity. Moreover, many other solutions found in the literature have also neglected the importance of the relative stiffness between the ground mass and support structure, probably owing to the relatively coarse meshes used in these studies. The analyses presented here show that relative stiffness may account for internal force discrepancies in the order of 60%. A dimensionless expression that takes all these parameters into account is presented as a good approximation for the load transfer mechanism at the tunnel face.

AnSBBR Applied to a Personal Care Industry Wastewater Treatment: Effects of Fill Time, Volume Treated Per Cycle, and Organic Load

A study was performed regarding the effect of the relation between fill time, volume treated per cycle, and influent concentration at different applied organic loadings on the stability and efficiency of an anaerobic sequencing batch reactor containing immobilized biomass on polyurethane foam with recirculation of the liquid phase (AnSBBR) applied to the treatment of wastewater from a personal care industry. Total cycle length of the reactor was 8 h (480 min). Fill times were 10 min in the batch operation, 4 h in the fed-batch operation, and a 10-min batch followed by a 4-h fed batch in the mixed operation. Settling time was not necessary since the biomass was immobilized and decant time was 10 min. Volume of liquid medium in the reactor was 2.5 L, whereas volume treated per cycle ranged from 0.88 to 2.5 L in accordance with fill time. Influent concentration varied from 300 to 1,425 mg COD/L, resulting in an applied volumetric organic load of 0.9 and 1.5 g COD/L.d. Recirculation flow rate was 20 L/h, and the reactor was maintained at 30 A degrees C. Values of organic matter removal efficiency of filtered effluent samples were below 71% in the batch operations and above 74% in the operations of fed batch followed by batch. Feeding wastewater during part of the operational cycle was beneficial to the system, as it resulted in indirect control over the conversion of substrate into intermediates that would negatively interfere with the biochemical reactions regarding the degradation of organic matter. As a result, the average substrate consumption increased, leading to higher organic removal efficiencies in the fed-batch operations.

AnSBBR Applied to the Treatment of Metalworking Fluid Wastewater: Effect of Organic and Shock Load

An investigation was performed regarding the application of a mechanically stirred anaerobic sequencing batch biofilm reactor containing immobilized biomass on inert polyurethane foam (AnSBBR) to the treatment of soluble metalworking fluids to remove organic matter and produce methane. The effect of increasing organic matter and reactor fill time, as well as shock load, on reactor stability and efficiency have been analyzed. The 5-L AnSBBR was operated at 30 A degrees C in 8-h cycles, agitation of 400 rpm, and treated 2.0 L effluent per cycle. Organic matter was increased by increasing the influent concentration (500, 1,000, 2,000, and 3,000 mg chemical oxygen demand (COD)/L). Fill times investigated were in the batch mode (fill time 10 min) and fed-batch followed by batch (fill time 4 h). In the batch mode, organic matter removal efficiencies were 87%, 86%, and 80% for influent concentrations of 500, 1,000, and 2,000 mgCOD/L (1.50, 3.12, and 6.08 gCOD/L.d), respectively. At 3,000 mgCOD/L (9.38 gCOD/L.d), operational stability could not be achieved. The reactor managed to maintain stability when a shock load twice as high the feed concentration was applied, evidencing the robustness of the reactor to potential concentration variations in the wastewater being treated. Increasing the fill time to 4 h did not improve removal efficiency, which was 72% for 2,000 mgCOD/L. Thus, gradual feeding did not improve organic matter removal. The concentration of methane formed at 6.08 gCOD/L was 5.20 mmolCH(4), which corresponded to 78% of the biogas composition. The behavior of the reactor during batch and fed-batch feeding could be explained by a kinetic model that considers organic matter consumption, production, and consumption of total volatile acids and methane production.

Influence of feed time and sulfate load on the organic and sulfate removal in an ASBR

The removal of sulfate and organic matter was assessed in an ASBR, which treated wastewater containing 500 mg COD L(-1) (3 g COD L(-1) d(-1)) in 8 h-cycles at 30 degrees C. The wastewater was enriched with sulfate at [COD/SO(4)(2-]) ratios of 1.34, 0.67 and 0.34 (8.8,4.5 and 2.2 gSO(4)(2-) L(-1) d(-1)). For each COD/[SO(4)(2-)] ratio fill times used were: 10 min (batch), 3 and 6 h (fed-batch), achieving sulfate reduction of 30%, 72% and 72% (COD/[SO(4)(2-)] of 1.34); 25%, 58% and 55% (COD/[SO(4)(2-)] of 0.67) and 23%, 37% and 27% (COD/[SO(4)(2-)] of 0.34), respectively, and organic matter removal of 87%, 68% and 80% (COD/[SO(4)(2-)] of 1.34); 78%, 75% and 69% (COD/[SO(4)(2-)] of 0.67) and 85%, 84% and 83% (COD/[SO(4)(2-)] of 0.34), respectively. The results showed that fed-batch operation improved sulfate reduction, whereas organic matter removals were similar for batch and fed-batch operation. In addition, increase in sulfate loading in the fed-batch operation improved organic matter removal. (C) 2010 Elsevier Ltd. All rights reserved.