Conformations and electronic structures of axially coordinated fullerene-porphyrin-fullerene triad (C60CHCOO)2-Sn(IV) porphyrin

The conformational (cis and trans) stability and electronic structures of (C(60)CHCOO)(2)-Sn(IV) porphyrin, recently synthesized as a novel fullerene-porphyrin-fullerene triad linked by metal axial coordination, have been studied by ab initio calculations. The cis conformer was found to be slightly more stable than the trans by 1.38 kcal/mol in the neutral compound. Upon the addition of an electron to the triad, the relative stability of the cis conformer was found to be higher (3.29 kcal/mol) than that in the neutral one. From the investigation of frontier molecular orbitals, for the cis conformer, it was found that the electrons are localized in HOMO of the porphyrin, while the electrons are localized in LUMO of the syn-fullerene. For the trans conformer, it was found that the electrons are localized in HOMO of the porphyrin, while the electrons are localized in LUMO of one of the two fullerene moieties, and the electrons are localized in LUMO2 of the other fullerene moiety, but the LUMO and LUMO2 have the same orbital energy. Thus, the PET may take place unidirectionally in the cis conformer from the porphyrin to the syn-fullerene, while it is bidirectional from the porphyrin to both of the fullerene moieties.     

Coverage-mediated suppression of blinking in solid state quantum dot conjugated organic composite nanostructures

Size-correlated single-molecule fluorescence measurements on CdSe quantum dots functionalized with oligo(phenylene vinylene) (OPV) ligands exhibit modified fluorescence intermittency (blinking) statistics that are highly sensitive to the degree of ligand coverage on the quantum dot surface. As evidenced by a distinct surface height signature, fully covered CdSe-OPV nanostructures (approximately 25 ligands) show complete suppression of blinking in the solid state on an integration time scale of 1 s. Some access to dark states is observed on finer time scales (100 ms) with average persistence times significantly shorter than those from ZnS-capped CdSe quantum dots. This effect is interpreted as resulting from charge transport from photoexcited OPV into vacant trap sites on the quantum dot surface. These results suggest exciting new applications of composite quantum dot/organic systems in optoelectronic systems.     

A Lewis acid-catalyzed formal [3 + 3] cycloaddition of alpha,beta-unsaturated aldehydes with 4-hydroxy-2-pyrone, diketones, and vinylogous esters

[reaction: see text] A Lewis acid-catalyzed formal cycloaddition of alpha,beta-unsaturated aldehydes with 6-methyl-4-hydroxy-2-pyrone, 1,3-diketones, and vinylogous silyl esters is described here.     

Applications of asymmetric hydrosilylations mediated by catalytic (DTBM-SEGPHOS)CuH

[reaction: see text] Several aryl ketone precursors useful in the synthesis of known physiologically active compounds have been reduced to the corresponding nonracemic alcohols. The previously reported combination of a catalytic quantity of (R)-(-)-DTBM-SEGPHOS-ligated CuH and stoichiometric PMHS is shown to be very effective in these asymmetric hydrosilylations.     

Theory of laser acceleration of light-ion beams from interaction of ultrahigh-intensity lasers with layered targets

Experiments at the LANL Trident facility demonstrated the production of monoenergetic ion beams from the interaction of an ultraintense laser with a target comprising a heavy ion substrate and thin layer of light ions. An analytic model is obtained that predicts how the mean energy and quality of monoenergetic ion beams and the energy of substrate ions vary with substrate material and light-ion layer composition and thickness. Dimensionless parameters controlling the dynamics are derived and the model is validated with particle-in-cell simulations and experimental data.     

Imaging spin-reorientation transitions in consecutive atomic Co layers on Ru(0001)

By means of spin-polarized low-energy electron microscopy, we show that the magnetic easy axis of one to three atomic-layer thick cobalt films on Ru(0001) changes its orientation twice during deposition: One-monolayer and three-monolayer thick films are magnetized in plane, while two-monolayer films are magnetized out of plane. The Curie temperatures of films thicker than one monolayer are well above room temperature. Fully relativistic calculations based on the screened Korringa-Kohn-Rostoker method demonstrate that only for two-monolayer cobalt films does the interplay between strain, surface, and interface effects lead to perpendicular magnetization.     

Universality of synchrony: critical behavior in a discrete model of stochastic phase-coupled oscillators

We present the simplest discrete model to date that leads to synchronization of stochastic phase-coupled oscillators. In the mean field limit, the model exhibits a Hopf bifurcation and global oscillatory behavior as coupling crosses a critical value. When coupling between units is strictly local, the model undergoes a continuous phase transition which we characterize numerically using finite-size scaling analysis. In particular, the onset of global synchrony is marked by signatures of the XY universality class, including the appropriate classical exponents beta and nu, a lower critical dimension d(lc) = 2, and an upper critical dimension d(uc) = 4.     

Some contributions to the model order reduction of large scale non-linear electric circuits

Model order Reduction (MOR) has become an ubiquitous technique in the simulation of large-scale dynamical systems (i.e. 10⁴ and more equations). One technique for non-linear MOR is the trajectory piecewise-linear approach (TPWL) [1]. TPWL approximates a non-linear differential system by a weighted sum of linear systems which have a significantly reduced number of equations. One open question is which weight representations provide physical meaning of the weighted sum [2]. In this article we propose two representations. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

INARCH(1) processes: Higher-order moments and jumps

The INARCH(1) model is a simple but practically relevant, two-parameter model for processes of overdispersed counts with an autoregressive serial dependence structure. We derive closed-form expressions for the joint (central) moments and cumulants of the INARCH(1) model up to order 4. These expressions are applied to derive the moments of jumps in INARCH(1) processes. We illustrate this kind of application with a real-data example, and outline further potential applications.