Adsorption of dicarboxylates on nano-sized gibbsite particles: effects of ligand structure on bonding mechanisms

The adsorption of the dicarboxylates o-phthalate, maleate, fumarate, malonate, and oxalate (representing ligands with the general composition ⁻O₂C---C_n---CO₂⁻; n=0, 1, or 2) on gibbsite were studied by means of quantitative batch adsorption experiments and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The interpretations of ATR-FTIR spectra were aided by comparison with IR spectra of solution species and by results from theoretical frequency calculations. The main objectives of the study were to identify the molecular level bonding mechanisms of the dicarboxylates to gibbsite, and to investigate how these were influenced by the composition and structure of the ligands. Carboxylates with n=2 formed predominantly outer sphere complexes, whereas the importance of inner sphere complexes progressively increased for n=1 and 0. The inner sphere structures were identified as mononuclear chelates with one oxygen from each carboxylate group bonded to Al(III) at the surface. This showed the importance of chelate ring structure for the formation of inner sphere surface complexes, with stabilities of the complexes increasing in the order seven-membered ring less than six-membered ring less than five-membered ring. For ligands with n=2 only small variations in surface speciation were observed as a function of steric factors; irrespective of the relative positions of the carboxylate groups and bulkiness of the ligands outer sphere bonding is the dominating adsorption mode. Adsorption experiments were also conducted with gibbsite particles exhibiting differences in shape and surface roughness. These experiments showed that inner sphere complexes were favored on the less well-developed and more irregular gibbsite particles.     

The supersymmetric WKB approximation of ring-shaped oscillator potential in r and θ dimensions with spherical polar coordinates

According to calculation of the energy spectrum of ring-shape oscillator potential by using the supersymmetric WKB approximation, it is shown that the energy spectrum of some noncentral separable potentials can be exactly obtained in r and θ dimensions by above method.     

Difference schemes on uniform grids performed by general discrete operators

Our aim is to set the foundations of a discrete vectorial calculus on uniform n-dimensional grids, that can be easily reformulated on general irregular grids. As a key tool we first introduce the notion of tangent space to any grid node. Then we define the concepts of vector field, field of matrices and inner products on the space of grid functions and on the space of vector fields, mimicking the continuous setting. This allows us to obtain the discrete analogous of the basic first order differential operators, gradient and divergence, whose composition define the fundamental second order difference operator. As an application, we show that all difference schemes, with constant coefficients, for first and second order differential operators with constant coefficients can be seen as difference operators of the form for suitable choices of q, and  . In addition, we characterize special properties of the difference scheme, such as consistency, symmetry and positivity in terms of q, and  .     

卤代对苝醌类光敏剂光敏活性影响的量子化学研究

以一种新型的醌类光敏剂—菌生素 (HMB)为模型化合物 ,利用量子化学从头算HF/ 6 31G和含时密度泛函TD B3LYP/ 6 31G方法计算研究了卤代作用对醌类光敏剂分子性质和光敏活性的影响 .结果发现 ,卤代作用降低了HMB母体的HOMO和LUMO能级 (EHOMO和ELUMO)及其差值△E ,随卤族元素从上到下 ,EHOMO和ELUMO呈增大趋势 ,而△E呈减小趋势 ,使得分子激发光谱有不同程度的红移 ,在增加PQP三重态量子产率的同时降低了分子最低三重激发态的能量 ,两种作用相互抵消 ,使得卤代物的 1O2 量子产率与母体相似 ;增加了分子的绝热电子亲合势 ,使分子产生O2 -的能力下降 ;卤原子的引入 ,降低了HMB母体分子内氢键的强度 ,同时使顺式构型的分子内质子传递势垒增大 ,而使反式构型势垒减小 .     

Motion Control by ZV Shaper Synthesis Extended for Fractional Systems and Its Application to CRONE Control

Shaping command input or preshaping is used for reducing system oscillation in motion control. Desired systems inputs are altered so that the system finishes the requested move without residual oscillation. This technique, developed by N.C. Singer and W.P. Seering, is used for example in the aerospace field, in particular in flexible structure control. This paper presents the study of ZV shaper for explicit fractional derivative systems (generalized derivative systems). A robustness study of ZV shaper is then presented and applied to improve second generation CRONE control response time. Results from simulation and from a DC motor bench are also given.     

Influence of the light illumination on thermoluminescence properties of PbWO4

The thermally stimulated properties of PbWO₄ in the temperature range 90–400 K have been investigated on undoped and terbium-doped crystals after X-ray irradiation at 90 K. Doping with terbium changes the concentration of shallow traps, which are responsible for retrapping free electrons and holes. Light illumination can change the distribution of the traps. The optically stimulated luminescence is observed. The influence of light illumination on the TSL curves and emission properties is studied. The possible mechanism of TSL phototransformation is discussed.     

On the determination of quark masses from the Dalitz plot for the decay η → π+π?π0

An experimental Dalitz plot distribution for the decay η → π ⁺ π ⁻ π ⁰ is fitted by the theoretical one obtained in chiral perturbation theory with unitarity corrections taken into account. The fit shows that the difference of light-quark masses is larger than is expected from electromagnetic mass differences of neutral and charged kaons. From Yadernaya Fizika, Vol. 67, No. 2, 2004, pp. 443–445. Original English Text Copyright ? 2004 by Martemyanov, Sopov. This article was submitted by the authors in English.