从头计算方法比较研究B_2Au_4,Al_2Au_4和BAlAu_4的几何和电子结构(英文)

Au/H相似性的研究是现代化学中的一个热门话题.我们从理论上报道Au/H相似的新成员:共价化合物B2Au4,离子化合物Al2Au4和BAl Au4.采用密度泛函和波函数理论方法对比研究了缺电子体系B2Au4、Al2Au4和BAl Au4的几何和电子结构.详细讨论了它们基态结构的轨道、适应性自然密度划分(Ad NDP)和电子局域函数(ELF)分析.计算结果表明稍微扭曲变形的C2B2Au4是基态结构,在这个共价化合物中含有两个B―Au―B三中心二电子(3c-2e)键.然而C3vAl+(Al Au4)-和C3vAl+(BAu4)-被研究证明是含有三个X―Au―Al三中心二电子键的类盐化合物(在Al2Au4中X=Al,BAl Au4中X=B).Al2Au4和BAl Au4是至今为止首例报道的在离子缺电子体系中含有金桥键的化合物.同时计算了B2Au4-、Al2Au4-和BAl Au4-阴离子基态结构的绝热剥离能和垂直剥离能,为实验表征提供依据.文中报道的金桥键为共价键和离子键相结合的缺电子体系提供了一个有趣的键合模式,有助于设计含有高度分散金原子的新材料和催化剂.     

A Cross-Entropy Approach to the Estimation of Generalized Linear Multilevel Models

In this article, we use the cross-entropy method for noisy optimization for fitting generalized linear multilevel models through maximum likelihood. We propose specifications of the instrumental distributions for positive and bounded parameters that improve the computational performance. We also introduce a new stopping criterion, which has the advantage of being problem-independent. In a second step we find, by means of extensive Monte Carlo experiments, the most suitable values of the input parameters of the algorithm. Finally, we compare the method to the benchmark estimation technique based on numerical integration. The cross-entropy approach turns out to be preferable from both the statistical and the computational point of view. In the last part of the article, the method is used to model the probability of firm exits in the healthcare industry in Italy. Supplemental materials are available online.     

Adaptive Catalytic Systems for Chemical Energy Conversion

The rapidly growing importance of green hydrogen and renewable carbon resources as essential feedstocks for sustainable chemical value chains opens room for disruptive innovations regarding chemical production processes. The fluctuation and variability associated with non-fossil energy and raw material supply holds many challenges for catalysts to cope with the resulting dynamics. However, many new opportunities also arise once catalyst design starts to aim at performance that is “adaptive” rather than “task-specific”. In this Scientific Perspective, we propose to define adaptivity in catalysis on the basis of three essential properties that are reversibility, rapidity, and robustness (R³ rule). Promising design strategies and selected examples are described to substantiate the scientific concept and to highlight its potential for chemical energy conversion.     

Adaptive neuro-fuzzy interference system modelling for chlorpyrifos removal with walnut shell biochar

Accumulation of chlorpyrifos (CP), a pesticide, causes a significant environmental problem in food, surface/ground waters further to human health. The removal of the CP pollutant in surface/wastewater could be achieved by biochar due to the improved physical and chemical properties. In this work, the CP removal capacities of biochar samples derived from walnut shells at various temperatures from 450 to 900 °C were investigated. The experiments were performed as laboratory batch type study and the adsorption efficiency was determined at various conditions such as adsorbent dosage (10–500 mg/L), sorbate concentrations (100–1500 µg/L), contact time (0–300 min), initial pH (3–10), and the number of recycle.By subtracting the pyrolysis temperature from 450 °C to 900 °C, the surface areas were found to increase from 12.9 m²/g to 353.3 m²/g, respectively.The 143 experimental data were evaluated by a pair of kinetics and isotherm models and the Adaptive Neural Fuzzy Inference System (ANFIS). The developed ANFIS model was 98.56% successful in predicting the CP removal efficiency depending on the adsorption conditions. Walnut Shell Biochar (WSBC) can be applied for CP adsorption with 86.64% removal efficiency under optimum adsorption conditions (adsorbent = 250 µg/L, sorbate = 1000 µg/L, pH = 7.07 and contact time 15 min) thanks to its improved porosity. It was determined that the biochar samples could be reused 5 times. Equilibrium adsorption was observed to conform to the Langmuir isotherm, and the maximum adsorption capacity for WSBC@900 was 3.536 mg/g.     

Adaptive Control of Nonlinear Dynamical Systems Using a Model Reference Approach

In this paper we consider using a model reference adaptive control approach to control nonlinear systems. We consider the controller design and stability analysis associated with these type of adaptive systems. Then we discuss the use of model reference adaptive control algorithms to control systems which exhibit nonlinear dynamical behaviour using the example of a Duffing oscillator being controlled to follow a linear reference model. For this system we show that if the nonlinearity is small then standard linear model reference control can be applied. A second example, which is often found in synchronization applications, is when the nonlinearities in the plant and reference model are identical. Again we show that linear model reference adaptive control is sufficient to control the system. Finally we consider controlling more general nonlinear systems using adaptive feedback linearization to control scalar nonlinear systems. As an example we use the Lorenz and Chua systems with parameter values such that they both have chaotic dynamics. The Lorenz system is used as a reference model and a single coordinate from the Chua system is controlled to follow one of the Lorenz system coordinates.     

Viscous waves and wave-structure interaction in a tank using adapting quadtree grids

Viscous waves and waves over a submerged cylinder in a stationary tank are simulated using a volume-of-fluid numerical scheme on adaptive hierarchical grids. A high resolution interface-capturing method is used to advect the free surface interface and the Navier–Stokes equations are discretised using finite volumes with collocated primitive variables and solved using a Pressure Implicit with Splitting of Operators (PISO) algorithm. The cylinder is modelled by using the technique of Cartesian cut cells. Results of flow of a single fluid past a cylinder at Reynolds number Re=100 are presented and found to agree well with experimental and other numerical data. Viscous free surface waves in a tank are simulated using uniform and quadtree grids for Reynolds numbers in the range from 2 to 2000, and the results compared against analytical solutions where available. The quadtree-based results are of the same accuracy as those on the equivalent uniform grids, and retain a sharp interface at the free surface while leading to considerable savings in both storage and CPU requirements. The nonlinearity in the wave is investigated for a selection of initial wave amplitudes. A submerged cylinder is positioned in the tank and its influence on the waves as well as the hydrodynamic loading on the cylinder is investigated.     

Adaptive unstructured finite element method for two-dimensional detonation simulations

A non-equilibrium reacting flow methodology has been added to a conservative, monotonic, compressible flow solver to allow numerical simulations of gas detonations. This flow solver incorporates unstructured dynamically adaptive meshes with the Finite Element Method – Flux Corrected Transport (FEM-FCT) scheme, which has shown excellent predictive capability of various non-reacting compressible flows. A two-step induction parameter model was used to model the combustion of the gas phase coupled with an energy release equation which was simulated with a point implicit finite element scheme. This combustion model was then applied to a two-dimensional detonation test case of a hypothetical fuel:oxygen mixture. The detonation simulation yielded two transverse waves which continued to propagate. This feature and the detonation shock speed mean and fluctuations were found to be grid-independent based on a resolution of about twenty elements within the average induction length. The resolution was efficiently achieved with the unstructured dynamically adaptive finite elements, which were three orders of magnitude less in number then required for uniform discretization. Received 26 August 1996 / Accepted 31 March 1997     

An adaptive updating full-Newton step interior-point algorithm with modified Newton direction

We adopt the self-adaptive strategy to update the barrier parameter of a feasible primal-dual interior-point algorithm. We obtain two adaptive updating methods, namely, cheap updates and sharp updates. We compare the effectiveness of the short updates with the adaptive update methods on some benchmark problems. The numerical results show that the sharp updates method is superior to short updates and cheap updates methods.