Optimal superconvergent one step quadratic spline collocation methods

We formulate new optimal quadratic spline collocation methods for the solution of various elliptic boundary value problems in the unit square. These methods are constructed so that the collocation equations can be solved using a matrix decomposition algorithm. The results of numerical experiments exhibit the expected optimal global accuracy as well as superconvergence phenomena. AMS subject classification (2000)  65N35, 65N22     

Polymorphism in PbBiOXO4 compounds (X=V, P, As): Part II—PbBiOPO4 and PbBiOAsO4 structures and characterization of related solid solutions

Reinvestigation of PbBiOXO₄ (X=V, P, As) thermal behaviour revealed a phase transition for V- and P-compounds, but no transition for the As-compound. As shown by single-crystal X-ray diffraction and high-resolution neutron powder diffraction, α-PbBiOVO₄ transforms to β-PbBiOVO₄ at 550 °C. The two PbBiOPO₄ varieties are isomorph to the vanadate forms, while PbBiOAsO₄ adopts the β-type structure whatever the temperature. PbBiP_1−xOAs_xO₄ and PbBiV_1−xOM_xO₄ (M=As, P, Cr, Mn) solid solutions display both triclinic and monoclinic domains, and the α→β transition temperature is a function of the substitution rate. The ionic conductivity of these compounds was investigated by impedance spectroscopy. The analysis of free space in the β-PbBiOVO₄ structure allows to propose a one-dimensional oxygen diffusion pathway along [010] when the temperature increases.     

Isomerization kinetics of small hydrocarbons in confinement

Chemical reactions are often carried out in nano-structured materials, which can enhance reactions due to their large specific surface area, their interactions with the reacting mixture and confinement effects. In this work, we present a systematic study of the effect that the geometrical restrictions imposed by the pore walls can have on reactions that involve a three dimensional rearrangement of the atoms in a molecule. In particular, we consider the isomerization of three 4-membered hydrocarbons—n-butane, 1-butene and 1,3-butadiene confined in carbon nanopores of slit geometry. Our results illustrate the fact that, in the molecular sieving limit, the reaction rates change as the double exponential of the pore size (Santiso et al., in J. Chem. Phys., 2007a, submitted), and therefore the transition rates in nanopores can be many orders of magnitude different from the corresponding bulk values. These results can be used as a guideline for the molecular-level design of improved catalytic materials.     

Interfacial change on morphological transitions in styrene-isoprene diblock copolymer

The specific interfacial area (S/V) and interfacial thickness in each microstructure of styrene-isoprene diblock copolymer were estimated by analyzing the deviations from Porod’s law. The thermally induced phase transitions proceeded from lamellae (L) to hexagonally ordered cylinder (HEX), via hexagonally perforated layer (HPL) and gyroid (G). The S/V ratio increased stepwise at the order-order transition (OOT) from L to HEX, via HPL and G. The S/V data can be utilized for OOT determination.     

Dynamics of Ice Surfaces

The dynamics of faceted and partially faceted single crystal and polycrystalline ice are reviewed with an emphasis on the manner in which microscopic effects produce macroscopic shapes. Our understanding of the former is rooted in the basic kinetics common to all materials and our pursuit of the latter is largely motivated by the striking patterns exhibited in the natural environment when water changes phase to become ice.     

The influence of peripheral ligand bulk on nitrogen activation by three‐coordinate molybdenum complexes—A theoretical study using the ONIOM method

Electronic structure methods have been combined with the ONIOM approach to carry out a comprehensive study of the effect of ligand bulk on the activation of dinitrogen with three‐coordinate molybdenum complexes. Calculations were performed with both density functional and CCSD(T) methods. Our results show that not only is there expected destabilization of the intermediate on the pathway due to direct steric interactions of the bulky groups, but also there is significant electronic destabilization as the size of the ligand increases. This latter destabilization is due to the inability of the molecule to accommodate a rotated amide group bound to the molybdenum once the amide reaches a certain size. This destabilization also leads to a clear preference for the triplet intermediate (rather than the singlet intermediate) for bulky substituents which is in agreement with experiment. Overall, the calculated reaction profile for the bulky substituents shows a good correlation with the available experimental data. © 2009 Wiley Periodicals, Inc. J Comput Chem 2009     

硅中浅杂质的激光感应光电导谱

首次采用光子能量小于硅中浅受主杂质电离能的可调谐远红外激光器作为激发源,获得了硅中浅受主杂质的光电导谱.可调谐半导体远红外激光器的调谐范围为380～500cm~(-1),光子流密度约10~(18)/cm~2·sec,用双光子跃迁对光电导谱进行了解释.对于Si:Al样品,光电导谱中的双峰分别相应于2P~1和2P~2中间态的双光子共振跃迁.也观察到了双光子透明的反共振现象.     

带阻尼项一维非等熵流方程组初边值问题解的收敛速度

研究了带阻尼项一维非等熵流方程组的初边值问题，利用能量估计的办法证明了整体解的存在性和得到在L2－模及L∞－模意义下解的大时间状态稳定性估计。