Electronic structure of sub-10 nm colloidal silica nanoparticles measured by in situ photoelectron spectroscopy at the aqueous-solid interface

X-Ray photoelectron spectroscopy has been extended to colloidal nanoparticles in aqueous solution using a liquid microjet in combination with synchrotron radiation, which allowed for depth-dependent measurements. Two distinct electronic structures are evident in the Si 2p photoelectron spectrum of 7 nm SiO(2)-nanoparticles at pH 10. A core-shell model is proposed where only the outermost layer of SiO(2) nanoparticles, which is mainly composed of deprotonated silanol groups, >Si-O(-), interacts with the solution. The core of the nanoparticles is not affected by the solvation process and retains the same electronic structure as measured in vacuum. Future opportunities of this new experiment are also highlighted.     

Radon hydrides: structure and bonding

Quantum chemical calculations, using gradient-correct density functional at the BP86 level in conjunction with TZ2P basis sets, have been carried out for the radon hydrides HRnY (with Y = F, Cl, Br, I, CCH, CN, and NC). The bonding in HRnY is studied using different bond ruptures, establishing the role of those stabilizing (and destabilizing) factors that prevent these species to be dissociated. Although all HRnY systems studied here are bound equilibrium structures, they are metastable species with respect to the HRnY → Rn + HY decomposition channel. However, the HRnY → H + Rn + Y reaction is endothermic. So, these results indicate the possibility to identify the radon hydrides in noble-gas matrices.     

The molecular mechanism of dual emission in terpyridine transition metal complexes--ultrafast investigations of photoinduced dynamics

Temperature dependent luminescence experiments are combined with femtosecond time-resolved transient absorption spectroscopy to decipher the photoinduced excited-state relaxation pathway in mononuclear Fe, Ru and Os terpyridine complexes bearing a conjugated chromophore within the ligand framework. The herein presented complexes constitute a class of coordination compounds, which overcome the poor emission properties commonly observed for most terpyridine transition metal complexes. As reported earlier, the complexes reveal dual emission at room temperature stemming from ligand centered and metal-to-ligand charge-transfer states. The molecular mechanism of the room temperature dual luminescence is addressed experimentally in this contribution. The experimental results indicate an ultrafast branching reaction within the excited-state manifold upon photoexcitation of the ligand-centered S(1) state. This branching occurs from a "hot" excited state geometry close to the Franck-Condon point of absorption and within ～100 fs, i.e. the temporal resolution of our experimental setup. The combination of ultrafast differential absorption experiments and temperature-dependent luminescence data allows not only to draw conclusions about the molecular mechanism underlying the observed dual emission but also to construct quantitative Jablonski diagrams and, thereby, to detail the excited-state topology determining the remarkable luminescence properties of the systems at hand.     

Ginzburg–Landau Vortices Driven by the Landau–Lifshitz–Gilbert Equation

A simplified model for the energy of the magnetization of a thin ferromagnetic film gives rise to a version of the theory of Ginzburg–Landau vortices for sphere-valued maps. In particular, we have the development of vortices as a certain parameter tends to 0. The dynamics of the magnetization are ruled by the Landau–Lifshitz–Gilbert equation, which combines characteristic properties of a nonlinear Schrödinger equation and a gradient flow. This paper studies the motion of the vortex centers under this evolution equation.     

Friction Drag Variation via Spanwise Transversal Surface Waves

The introduction of spanwise velocity is a promising technique to effect the near-wall turbulent flow field to influence friction drag. However, the essential physical mechanism which significantly reduces friction drag has not been understood, yet. It is the objective of this numerical study to improve the fundamental knowledge on the drag reduction mechanism. The investigation is based on spanwise traveling transversal surface waves which are applied to modify the near-wall flow field and to influence friction drag. Two actuation configurations are analyzed in detail. Compared with an unactuated flat plate boundary layer simulation the first wave setup, which represents a low frequency wave at an amplitude larger than the viscous sublayer, leads to a reduced wall-shear stress resulting in friction drag reduction of up to 9%. The second wave setup, which possesses a higher frequency and an amplitude in the range of the viscous sublayer, yields an increase of friction drag of about 8%. Unlike previous investigations which focus on excitation setups to lower friction drag, the comparison of the two wave setups in this study allows to identify the effects which on the one hand, lead to drag reduction and on the other hand, result in drag increase. That is, due to the pronounced differences the major effects determining the friction distribution are more evident. The two key features for drag reduction are the damping of the wall-normal vorticity fluctuations above the entire surface and the decrease of turbulence production. Furthermore, the effect of rearranging streamwise vorticity, which has been stated to be responsible for drag reduction, is found to occur at increasing and decreasing drag, i.e., it is not the effect that lowers the friction drag.     

The commutation relation <Emphasis Type="Italic">xy</Emphasis>=<Emphasis Type="Italic">qyx</Emphasis>+<Emphasis Type="Italic">hf</Emphasis>(<Emphasis Type="Italic">y</Emphasis>) and Newton’s binomial formula

Let x and y be two variables satisfying the commutation relation xy=qyx+hf(y), where f(y) is a polynomial. In this paper, using Young diagrams and generating functions techniques, we study the binomial formula (x+y) ⁿ and we present an identity for x ^m y. The connection to Operator Calculus is discussed and several special cases are treated explicitly.     

Generalized graph entropies

This article deals with generalized entropies for graphs. These entropies result from applying information measures to a graph using various schemes for defining probability distributions over the elements (e.g., vertices) of the graph. We introduce a new class of generalized measures, develop their properties, compute the measures for selected graphs, and briefly discuss potential applications to classification and clustering problems. © 2011 Wiley Periodicals, Inc. Complexity, 17,45–50, 2011     

Convergence Analysis of the Implicit Euler-discretization and Sufficient Conditions for Optimal Control Problems Subject to Index-one Differential-algebraic Equations

For optimal control problems subject to index-one differential-algebraic equations in semi-explicit form we discuss second order sufficient conditions in form of a coercivity condition taking into account the two-norm discrepancy. Furthermore we introduce a related Riccati-type and Legendre-Clebsch condition which are sufficient for the validity of the coercivity condition. Using the implicit Euler-discretization we approximate the optimal control problem and analyze the convergence of solutions of the local minimum principle for the discretized optimal control problem by applying the general convergence framework of Stetter, which requires the discretization method to be continuous, consistent, and stable.