Comparative ab initio studies of small tin and lead clusters

We have performed ab initio total-energy pseudopotential calculations on neutral and negatively charged Snn and Pb_n (n = 3 ? 10) clusters. The lowest energy structures have been determined for all clusters, and the stabilities of neutral clusters were investigated by comparing their evaporation energies and stability functions. Clusters with n = 7,10 were found to be most stable while the clusters with n = 8 and Pb_s were much less stable, in agreement with features of the observed mass spectra. Calculations on Sn^?_n and Pb^?_n show that both atomic and electronic structures of a neutral cluster change substantially upon charging. The densities of states of Sn^?_n clusters reproduce the main features of the experimental photoelectron spectra. The agreement is poorer for Pb^?_n clusters where the calculations underestimate the separation between energy levels which we think is due to the larger spin-orbit splitting in Pb, which was neglected in the calculations. We found that the differences between Sn and Pb clusters cannot be completely addressed without a more complete accounting of relativistic effects. The electron affinities of Sn_n and Pb_n clusters have also been calculated and the results agree fairly well with experimental values. Finally we considered Sn^2?₄ and Pb^2?₄ clusters and related the results to the formation of Zintl anions in liquid alkali-Sn and alkali-Pb alloys.     

Optical absorption and fluorescence investigation of the precipitated phases of Eu2+ in KBr single crystals

Europium precipitation in monocrystalline KBR has been studied using optical absorption and photoluminescence techniques. The annealing of quenched samples at temperatures below 100°C produces the growth of an emission band peaking at 433 nm which appears to be related with the presence of Suzuki-type precipitates in the crystals. The aging at higher temperatures, however, produces the appearence in the emission spectrum of two other bands peaking at 427 and 459 nm. The data presented in this paper strongly suggest that the former band is associated with the stable dihalide phase EuBr₂ in the host KBr, while the latter is due to a metastable precipitate whose structure appears to be quite similar to that of europium bromide. Some of the characteristics of the second phase precipitates were obtained by measuring the crystal field splitting (10 Dq) of the 4f⁶5d configuration of the Eu²⁺ ions in each one of them.     

A TDDFT study of the excited states of DNA bases and their assemblies

We present a detailed study of the optical absorption spectra of DNA bases and base pairs, carried out by means of time dependent density functional theory. The spectra for the isolated bases are compared to available theoretical and experimental data and used to assess the accuracy of the method and the quality of the exchange-correlation functional. Our approach turns out to be a reliable tool to describe the response of the nucleobases. Furthermore, we analyze in detail the impact of hydrogen bonding and pi-stacking in the calculated spectra for both Watson-Crick base pairs and Watson-Crick stacked assemblies. We show that the reduction of the UV absorption intensity (hypochromicity) for light polarized along the base-pair plane depends strongly on the type of interaction. For light polarized perpendicular to the basal plane, the hypochromicity effect is reduced, but another characteristic is found, namely a blue shift of the optical spectrum of the base-assembly compared to that of the isolated bases. The use of optical tools as fingerprints for the characterization of the structure (and type of interaction) is extensively discussed.     

Nonwandering set of points of skew-product maps with base having closed set of periodic points

The aim of the present paper is to study the structure of the nonwandering set of points Ω() for the skew-product maps of the unit square , (x,y)→(f(x),g(x,y)), with base f having closed set of periodic points. For every and every point (x,y) with x periodic of period p_x by f and y not chain recurrent of F^p_x|_Ix, where , we prove that (x,y)Ω(F). On the other hand we construct a map with an isolated fixed point x₀ of f and y₀Ω(F|_Ix0) such that (x₀,y₀)Ω(F₀).     

Nonlinear modeling and control of slosh in liquid container transfer via a PPR robot

This paper studies the point-to-point liquid container transfer control problem for a PPR robot. The robot manipulator is represented as three rigid links, and the liquid slosh dynamics are included using a multi-mass-spring model. It is assumed that two forces and a torque applied to the prismatic joints and the revolute joint, respectively, are available as control inputs. The objective is to control the robot end-effector movement while suppressing the sloshing modes. A nonlinear mathematical model that reflects all of these assumptions is first introduced. Then, Lyapunov-based feedback controllers are designed to achieve the control objective. Two cases are considered: partial-state feedback that does not use slosh state information and full-state feedback that uses both robot state and slosh state measurements or estimations. Computer simulations are included to illustrate the effectiveness of the proposed control laws.     

Optimization methodology assessment for the inlet velocity profile of a hydraulic turbine draft tube: part II—performance evaluation of draft tube model

Computational Fluids Dynamics (CFD) tools guide engineers and designers to estimate the performance of new designs. However, a CFD analysis can be very time-consuming depending mainly on the grid size and domain complexity. Thus, this paper aims to describe the tools used to evaluate and compare the performance of different 3D draft tube models for reducing the time-effort needed in an optimization procedure. The results presented here, are the second part of an overall research to establish a global optimization methodology to improve the performance of an hydraulic draft tube through the inlet velocity profile. Previously, three steps of optimization methodology to minimize the energy losses were studied: the inlet velocity profile parameterization, the numerical optimization set-up and the objective function validation. In the latter step, a global optimization method called Multi Island Genetic Algorithm (MIGA) was considered, which requires a large number of iterations before producing a reliable result. This step is able to identify an efficient inlet velocity profile to minimize the energy losses through the draft tube model. However, each iteration is expensive in terms of computational time due to the need for 3D Navier–Stokes (NS) computations to evaluate each profile’s fitness. Thus, in this work the methodology attempts to accelerate the optimization process with accurate results. In order to achieve the goal, the grid size of the 3D draft tube model was minimized, resulting in a much lower computational cost. Specifically, the draft tube calculations were performed on a sequence of five different grids each having approximately twice the number of elements compared to the previous. The measurements of the sensitivity of the draft tube performance quantities to the change of the inlet velocity parameters during the process showed that, in spite of the numerical difference between its performance, the results have the same tendency. Consequently, the 3D draft tube numerical model with a minimal grid size, is reliable and left record of its capabilities for being integrated in the optimization process.     

Scientometric Picture of the Evolution of the Literature of Automation in Spectroscopy and Its Current State

The current study focuses on the status of automation and mechanization in spectroscopy for analytical chemistry publications compiled during the period 1980–2006, in Analytical Abstracts. Flow injection analysis (FIA), sequential injection analysis (SIA), multicommutation, and monosegmented and segmented flow strategies were considered. For assessing the evolution of scientific productivity, the total number of publications concerned with the different methodologies was evaluated. In order to provide a picture of the state of the art of this field, the most important journals, the most active authors, and the most productive countries in the field of automation were evaluated in the period of the first years of this century.     

Optical saturation driven by exciton confinement in molecular chains: a time-dependent density-functional theory approach

We identify excitonic confinement in one-dimensional molecular chains (i.e., polyacetylene and H2) as the main driving force for the saturation of the chain polarizability as a function of the number of molecular units. This conclusion is based on first principles time-dependent density-functional theory calculations using a recently developed exchange-correlation kernel that accounts for excitonic effects. The failure of simple local and semilocal functionals is shown to be linked to the lack of memory effects, spatial ultranonlocality, and self-interaction corrections. These effects get smaller as the gap reduces, in which case such simple approximations do perform better.     

Fast Exfoliation and Functionalisation of Two‐Dimensional Crystalline Carbon Nitride by Framework Charging

Two‐dimensional (2D) layered graphitic carbon nitride (gCN) nanosheets offer intriguing electronic and chemical properties. However, the exfoliation and functionalisation of gCN for specific applications remain challenging. We report a scalable one‐pot reductive method to produce solutions of single‐ and few‐layer 2D gCN nanosheets with excellent stability in a high mass yield (35 %) from polytriazine imide. High‐resolution imaging confirmed the intact crystalline structure and identified an AB stacking for gCN layers. The charge allows deliberate organic functionalisation of dissolved gCN, providing a general route to adjust their properties.