Spin gaps and spin-flip energies in density-functional theory

Energy gaps are crucial aspects of the electronic structure of finite and extended systems. Whereas much is known about how to define and calculate charge gaps in density-functional theory (DFT), and about the relation between these gaps and derivative discontinuities of the exchange-correlation functional, much less is known about spin gaps. In this paper we give density-functional definitions of spin-conserving gaps, spin-flip gaps and the spin stiffness in terms of many-body energies and in terms of single-particle (Kohn-Sham) energies. Our definitions are as analogous as possible to those commonly made in the charge case, but important differences between spin and charge gaps emerge already on the single-particle level because unlike the fundamental charge gap spin gaps involve excited-state energies. Kohn-Sham and many-body spin gaps are predicted to differ, and the difference is related to derivative discontinuities that are similar to, but distinct from, those usually considered in the case of charge gaps. Both ensemble DFT and time-dependent DFT (TDDFT) can be used to calculate these spin discontinuities from a suitable functional. We illustrate our findings by evaluating our definitions for the Lithium atom, for which we calculate spin gaps and spin discontinuities by making use of near-exact Kohn-Sham eigenvalues and, independently, from the single-pole approximation to TDDFT. The many-body corrections to the Kohn-Sham spin gaps are found to be negative, i.e., single-particle calculations tend to overestimate spin gaps while they underestimate charge gaps.

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.

Theory of nitride oxide adsorption on transition metal (111) surfaces: a first-principles investigation

In this work, we report a density functional theory study of nitric oxide (NO) adsorption on close-packed transition metal (TM) Rh(111), Ir(111), Pd(111) and Pt(111) surfaces in terms of adsorption sites, binding mechanism and charge transfer at a coverage of Theta(NO) = 0.25, 0.50, 0.75 monolayer (ML). Based on our study, an unified picture for the interaction between NO and TM(111) and site preference is established, and valuable insights are obtained. At low coverage (0.25 ML), we find that the interaction of NO/TM(111) is determined by an electron donation and back-donation process via the interplay between NO 5 sigma/2 pi* and TM d-bands. The extent of the donation and back-donation depends critically on the coordination number (adsorption sites) and TM d-band filling, and plays an essential role for NO adsorption on TM surfaces. DFT calculations shows that for TMs with high d-band filling such as Pd and Pt, hollow-site NO is energetically the most favorable, and top-site NO prefers to tilt away from the normal direction. While for TMs with low d-band filling (Rh and Ir), top-site NO perpendicular to the surfaces is energetically most favorable. Electronic structure analysis show that irrespective of the TM and adsorption site, there is a net charge transfer from the substrate to the adsorbate due to overwhelming back-donation from the TM substrate to the adsorbed NO molecules. The adsorption-induced change of the work function with respect to bare surfaces and dipole moment is however site dependent, and the work function increases for hollow-site NO, but decreases for top-site NO, because of differences in the charge redistribution. The interplay between the energetics, lateral interaction and charge transfer, which is element dependent, rationalizes the structural evolution of NO adsorption on TM(111) surfaces in the submonolayer regime.

Structural control of gold nanoparticles self-assemblies by layer-by-layer process

This work presents a novel way to introduce gold nanoparticles (Au NPs) in a multilayer polymer produced by the layer-by-layer (LbL) assembling technique. The technique chosen shows that, depending on the pH used, different morphological structures can be obtained from monolayer or bilayer Au NPs. The MEIS and RBS techniques allowed for the modelling of the interface polymer-NPs, as well as the understanding of the interaction of LbL system, when adjusting the pH in weak polyelectrolytes. The process reveals that the optical properties of multilayer systems could be fine-tuned by controlling the addition of metallic nanoparticles, which could also modify specific polarization responses.

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.

Evaluation of biologic occupational risk control practices: Quality indicators development and validation

Background: There is growing demand for the adoption of qualification systems for health care practices. This study is aimed at describing the development and validation of indicators for evaluation of biologic occupational risk control programs. Methods: The study involved 3 stages: (1) setting up a research team, (2) development of indicators, and (3) validation of the indicators by a team of specialists recruited to validate each attribute of the developed indicators. The content validation method was used for the validation, and a psychometric scale was developed for the specialists` assessment. A consensus technique was used, and every attribute that obtained a Content Validity Index of at least 0.75 was approved. Results: Eight indicators were developed for the evaluation of the biologic occupational risk prevention program, with emphasis on accidents caused by sharp instruments and occupational tuberculosis prevention. The indicators included evaluation of the structure, process, and results at the prevention and biologic risk control levels. The majority of indicators achieved a favorable consensus regarding all validated attributes. Conclusion: The developed indicators were considered validated, and the method used for construction and validation proved to be effective.

Control of interceptive actions is based on expectancy of time to target arrival

In this study the hypothesis that interceptive movements are controlled on the basis of expectancy of time to target arrival was tested. The study was conducted through assessment of temporal errors and kinematics of interceptive movements to a moving virtual target. Initial target velocity was kept unchanged in part of the trials, and in the others it was decreased 300 ms before the due time of target arrival at the interception position, increasing in 100 ms time to target arrival. Different probabilities of velocity decrease ranging from 25 to 100% were compared. The results revealed that while there were increasing errors between probabilities of 25 and 75% for unchanged target velocity, the opposite relationship was observed for target velocity decrease. Kinematic analysis indicated that movement timing adjustments to target velocity decrease were made online. These results support the conception that visuomotor integration in the interception of moving targets is mediated by an internal forward model whose weights can be flexibly adjusted according to expectancy of time to target arrival.

Postural control during prolonged standing in persons with chronic low back pain

Prolonged standing has been associated with the onset of low back pain symptoms in working populations. So far, it is unknown how individuals with chronic low back pain (CLBP) behave during prolonged unconstrained standing (PS). The aim of the present study was to analyze the control of posture by subjects with CLBP during PS in comparison to matched healthy adults. The center of pressure (COP) position of 12 CLBP subjects and 12 matched healthy controls was recorded in prolonged standing (30 min) and quiet stance tasks (60 s) on a force plate. The number and amplitude of COP patterns, the root mean square (RMS), speed, and frequency of COP sway were analyzed. Statistical analyses showed that CLBP subjects produced less Postural changes in the antero-posterior direction with decreased postural sway during the prolonged standing task in comparison to the healthy group. Only CLBP subjects were influenced by the prolonged standing task, as demonstrated by their increased COP RMS, COP speed and COP frequency in the quiet standing trial after the prolonged standing task in comparison to the pre-PS trial. The present study provides additional evidence that individuals with CLBP might have altered sensory-motor function. Their inability to generate responses similar to those of healthy subjects during prolonged standing may contribute to CLBP persistence or an increase risk of recurrent back pain episodes. Moreover, quantification of postural changes during prolonged standing could be useful to identify CLBP subjects prone to postural control deficits. (C) 2008 Elsevier B.V. All rights reserved.

Complexity of human postural control in young and older adults during prolonged standing

Aging is known to have a degrading influence on many structures and functions of the human sensorimotor system. The present work assessed aging-related changes in postural sway using fractal and complexity measures of the center of pressure (COP) dynamics with the hypothesis that complexity and fractality decreases in the older individuals. Older subjects (68 +/- 4 years) and young adult subjects (28 +/- 7 years) performed a quiet stance task (60 s) and a prolonged standing task (30 min) where subjects were allowed to move freely. Long-range correlations (fractality) of the data were estimated by the detrended fluctuation analysis (DFA); changes in entropy were estimated by the multi-scale entropy (MSE) measure. The DFA results showed that the fractal dimension was lower for the older subjects in comparison to the young adults but the fractal dimensions of both groups were not different from a 1/f noise, for time intervals between 10 and 600 s. The MSE analysis performed with the typically applied adjustment to the criterion distance showed a higher degree of complexity in the older subjects, which is inconsistent with the hypothesis that complexity in the human physiological system decreases with aging. The same MSE analysis performed without adjustment showed no differences between the groups. Taken all results together, the decrease in total postural sway and long-range correlations in older individuals are signs of an adaptation process reflecting the diminishing ability to generate adequate responses on a longer time scale.

Effect of bandwidth knowledge of results on the learning of a grip force control task

An experiment was conducted to investigate the persistence of the effect of ""bandwidth knowledge of results (KR)"" manipulated during the learning phase of performing a manual force-control task. The experiment consisted of two phases, an acquisition phase with the goal of maintaining 60% maximum force in 30 trials, and a second phase with the objective of maintaining 40% of maximum force in 20 further trials. There were four bandwidths of KR: when performance error exceeded 5, 10, or 15% of the target, and a control group (0% bandwidth). Analysis showed that 5, 10, and 15% bandwidth led to better performance than 0% bandwidth KR at the beginning of the second phase and persisted during the extended trials.

Inter-individual variability in temporal structure of the basketball shoot

This study analyzed inter-individual variability of the temporal structure applied in basketball throwing. Ten experienced male athletes in basketball throwing were filmed and a number of kinematic movement parameters analyzed. A biomechanical model provided the relative timing of the shoulder, elbow and wrist joint movements. Inter-individual variability was analyzed using sequencing and relative timing of tem phases of the throw. To compare the variability of the movement phases between subjects a discriminant analysis and an ANOVA were applied. The Tukey test was applied to determine where differences occurred. The significance level was p = 0.05. Inter-individual variability was explained by three concomitant factors: (a) a precision control strategy, (b) a velocity control strategy and (c) intrinsic characteristics of the subjects. Therefore, despite the fact that some actions are common to the basketball throwing pattern each performed demonstrated particular and individual characteristics.

Effects of medium supplementation and pH control on lactic acid production from brewer`s spent grain

A cellulose pulp obtained by chemical pre-treatment of brewer`s spent grain was saccharified by a commercial cellulase preparation and the produced hydrolysate (50 g/l glucose) was fermented to lactic acid by Lactobacillus delbrueckii. The effects of pH control and nutrient supplementation of the hydrolysate on fermentation performance were investigated. Addition of 5g/l yeast extract enhanced the lactic acid volumetric productivity that attained 0.53 g/l h, value 18% higher than that obtained from non-supplemented hydrolysate. Addition of the MRS broth medium components (except the carbon source) was still better, providing a productivity of 0.79 g/l h. In all the cases, the lactic acid yield factor was of 0.7 g/g glucose consumed, but the fermentations stopped after 24 h due to the pH drop from 6.0 to 4.2, resulting in large amounts of residual glucose (38-41 g/l). Fermentation runs pH-controlled at 6.0 gave better results than those where the initial pH was not further controlled. The best result, 35.54 g/l lactic acid (0.99 g/g glucose consumed) was obtained during the pH-controlled fermentation of hydrolysate medium supplemented with MRS components. The volumetric productivity at the end of this fermentation was 0.59 g/l h, with a maximum of 0.82 g/l h during the first 12 h. (c) 2008 Elsevier B.V. All rights reserved.

City tuberculosis control coordinators` perspectives of patient adherence to DOT in Sao Paulo State, Brazil, 2005

SETTING: Thirty-six priority cities in Sao Paulo State, Brazil, with a high incidence of tuberculosis (TB) cases, deaths and treatment default. OBJECTIVE: To identify the perspectives of city TB control coordinators regarding the most important components of adherence strategies adopted by health care teams to ensure patient adherence in 36 priority cities in the State of Sao Paulo, Brazil. DESIGN: Qualitative research with semi-structured interviews conducted with the coordinators of the National TB Control Programme involved in the management of TB treatment services in the public sector. RESULTS: The main issues thought to influence adherence to directly observed treatment (DOT) by coordinators include incentives and benefits delivered to patients, patient-health care worker bonding and comprehensive care, the encouragement given by others to follow treatment (family, neighbours and health professionals), and help provided by health professionals for patients to recover their self-esteem. CONCLUSION: The main aspects mentioned by city TB control coordinators regarding patient adherence to treatment and to DOT in Sao Paulo are improvements in communications, relationships based on trust, a humane approach and including the patients in the decision-making process concerning their health.

Embedded DSP-Based Compact Fuzzy System and Its Application for Induction-Motor V/f Speed Control

This paper presents a compact embedded fuzzy system for three-phase induction-motor scalar speed control. The control strategy consists in keeping constant the voltage-frequency ratio of the induction-motor supply source. A fuzzy-control system is built on a digital signal processor, which uses speed error and speed-error variation to change both the fundamental voltage amplitude and frequency of a sinusoidal pulsewidth modulation inverter. An alternative optimized method for embedded fuzzy-system design is also proposed. The controller performance, in relation to reference and load-torque variations, is evaluated by experimental results. A comparative analysis with conventional proportional-integral controller is also achieved.