Theoretical insight of adsorption thermodynamics of multifunctional molecules on metal surfaces

Adsorption thermodynamics based on density functional theory (DFT) calculations are exposed for the interaction of several multifunctional molecules with Pt and Au(1 1 0)-(1 × 2) surfaces. The Gibbs free adsorption energy explicitly depends on the adsorption internal energy, which is derived from DFT adsorption energy, and the vibrational entropy change during the chemisorption process. Zero-point energy (ZPE) corrections have been systematically applied to the adsorption energy. Moreover the vibrational entropy change has been computed on the basis of DFT harmonic frequencies (gas and adsorbed phases, clean surfaces), which have been extended to all the adsorbate vibrations and the metallic surface phonons. The phase diagrams plotted in realistic conditions of temperature (from 100 to 400 K) and pressure (0.15 atm) show that the ZPE corrected adsorption energy is the main contribution. When strong chemisorption is considered on the Pt surface, the multifunctional molecules are adsorbed on the surface in the considered temperature range. In contrast for weak chemisorption on the Au surface, the thermodynamic results should be held cautiously. The systematic errors of the model (choice of the functional, configurational entropy and vibrational entropy) make difficult the prediction of the adsorption-desorption phase boundaries.     

Evaluation of Commodity Trading Advisors using fixed and variable and benchmark models

This paper examines the performance of Commodity Trading Advisors (CTAs) using fixed and variable benchmarking models. In order to avoid the troublesome passive and active commodity and managed futures benchmarks (indices) when examining the performance of CTAs, we innovate by using data envelopment analysis (DEA). Because this alternative class has non-linear returns due to long/short positions, and derivatives (i.e., dynamic trading strategies), DEA can alleviate the problems usually associated with these indices. The effectiveness of using benchmarking models in a DEA setting will provide investors with an alternative technique in assessing the performance and identifying efficient CTAs.     

Solved and unsolved problems in surface structure determination

The range of surface structural problems of interest in understanding the physics and chemistry of solid surfaces is reviewed with reference to the available methods and their strengths and limitations. Key challenges being addressed currently concern the achievable precision of measurements and their physical and chemical significance, and the complexity of the problems which may be solved. Past progress and future problems are illustrated with a series of examples ranging from the relaxation of simple clean metal surfaces through complex semiconductor reconstructions to large molecular adsorption and coadsorption systems and complex adsorbate-induced reconstructions. The strengths and limitations of scanning tunnelling microscopy as a complement to true quantitative structural methods are discussed, as is the role of chemical state specificity and elemental specificity in solving complex molecular adsorbate systems.     

一种区间数的因子分析技术及其在证券市场中的应用

传统的因子分析技术能够有效地对高维变量空间进行降维处理,但它对于样本空间却缺乏行之有效的降维效果.为了解决这一问题,一种针对大量样本数据、新的因子分析技术———区间数因子分析技术(intervaldatafactoranalysis,IFA)被提出并得到了迅速的发展。IFA方法对传统的数据概念做了本质性的扩张,运用'数据打包'的理念,对海量原始数据在不破坏其原有内在逻辑关系的前提下,可以进行变量和样本点维度的双重降维。本文详细阐述了区间数因子分析技术的原理,并以中国股票市场为案例研究背景,结果表明IFA分析技术对大规模多维数据系统做综合简化是十分有效的。     

RESTRICTION RESPECTUEUSE ET RECONSTRUCTION DES CHAINES ET DES RELATIONS INFINITES

We show a faithful restriction theorem among infinite chains which implies a reconstructibility conjecture of Halin. This incite us to study the reconstructibility in the sense of Fraïssé and to prove it for orders of cardinality infinite or ≥ 3 and for multirelations of cardinality infinite or ≥ 7, what improves the theory obtained by G. Lopez in the finite case. For this work we had to study the infinite classes of difference which have to be a linear order of type ω, ω* or ω* + ω; this complete the theory made by G. Lopez for the finite case ([13]). We show also Ulam-reconstructibility for linear orders which have a fixed point.     

On accurate boundary conditions for a shape sensitivity equation method

This paper studies the application of the continuous sensitivity equation method (CSEM) for the Navier–Stokes equations in the particular case of shape parameters. Boundary conditions for shape parameters involve flow derivatives at the boundary. Thus, accurate flow gradients are critical to the success of the CSEM. A new approach is presented to extract accurate flow derivatives at the boundary. High order Taylor series expansions are used on layered patches in conjunction with a constrained least‐squares procedure to evaluate accurate first and second derivatives of the flow variables at the boundary, required for Dirichlet and Neumann sensitivity boundary conditions. The flow and sensitivity fields are solved using an adaptive finite‐element method. The proposed methodology is first verified on a problem with a closed form solution obtained by the Method of Manufactured Solutions. The ability of the proposed method to provide accurate sensitivity fields for realistic problems is then demonstrated. The flow and sensitivity fields for a NACA 0012 airfoil are used for fast evaluation of the nearby flow over an airfoil of different thickness (NACA 0015). Copyright © 2005 John Wiley & Sons, Ltd.     

Sulfur adsorption on Fe(1 1 0): a DFT study

The adsorption of atomic S on the Fe(1 1 0) surface is examined using density functional theory (DFT). Three different adsorption sites are considered, including the atop, hollow and bridge sites and the S is adsorbed at a quarter monolayer coverage in a p(2 × 2) arrangement. The hollow site is found to be the most stable, followed by the bridge and atop sites. At all three sites, S adsorption results in relatively minor surface reconstruction, with the most significant being that for the hollow site, with lateral displacements of 0.09 Å. Comparisons between S-adsorbed and pure Fe surfaces revealed reductions in the magnetic moments of surface-layer Fe atoms in the vicinity of the S. At the hollow site, the presence of S causes an increase in the surface Fe d-orbital density of states between 4 and 5 eV. However, S adsorption has no significant effect on the structure and magnetic properties of the lower substrate layers.     

Implementation and experimental study on fast object modeling based on multiple structured stripes

In this paper, a practical structured light-based system for fast object modeling and reconstruction is reported. The system consists of an off-the-shelf digital projector, a video camera and a turntable. The system calibration is implemented accurately and automatically by taking a single image of an illuminated calibration template. The multiple color light stripes emitted by the projector adopt only three colors and the color can be modified easily according to the surface texture of the object. This makes the system widely applicable in many situations, and the assumption about color neutrality, which is a limitation to other similar systems, can be largely relaxed. The registration and merging algorithm is greatly simplified by employing a turntable. The validity and high accuracy of the method are demonstrated by extensive real experiments.     

A statistical study of the analysis of congested spectra by total spectrum fitting

Heavily overlapped, or congested spectra often display much structure but few individual “lines.” Methods have been devised for analyzing such spectra through nonlinear least-squares fitting of the intensity as a function of wavelength or wavenumber. Such total spectrum fitting (TSF) methods are examined statistically for a simple diatomic model and compared with the standard “measure-assign-fit” (MAF) approach in use since the dawn of spectroscopy. Monte Carlo computations on typically 1000 synthetic spectra at a time verify that the predictions of the variance-covariance matrix are reliable under many circumstances. However in regions where the P and R branches double up, the predicted standard errors in the key spectroscopic constants rise sharply and greatly exceed estimates from the Monte Carlo ensemble statistics. In the same regions, the MAF method actually gives better precision. However, for imperfectly overlapped R and P branches, the MAF standard errors are typically three times larger than the TSF values; moreover, the MAF statistical errors are dwarfed by bias. The TSF approach, while clearly superior in these tests, has a practical drawback: it, too, can give significant bias if the spectra are analyzed with an incorrect model, as illustrated here through calculations employing the wrong function to describe the spectral lineshape.     

How I Do It: Miniplate Reconstruction of the Lateral Thyroid Lamina: One-Stage Restoration of Voice After Teflon Granuloma Resection

This case report describes a one-stage technique for long-term voice restoration and laryngeal reconstruction in the treatment of Teflon (Dupont, Wilmington, Delaware) granuloma. A patient who presented with severe dysphonia underwent resection of a Teflon granuloma via a lateral laryngotomy. A pedicled strap muscle flap was used to reconstruct the paraglottic space. The muscle flap was positioned through the lateral laryngotomy with direct endoscopic visualization of the endolarynx to ensure correct vertical positioning and medialization of the vocal fold. The muscle flap was secured in this position with suture fixation. The trapdoor piece of cartilage that was elevated to create the window in the lateral thyroid lamina was repositioned over the pedicled muscle flap and reinforced with a titanium miniplate, which was secured to the remaining thyroid cartilage. The patient had excellent voice results and has not required revision or augmentation. Reinforcement of the lateral thyroid lamina using titanium miniplate fixation helps to stabilize the muscle pedicle flap and the position of the vocal fold, in this case resulting in good long-term voice results after a single-stage reconstruction.