Multistability and the control of complexity

We show how multistability arises in nonlinear dynamics and discuss the properties of such a behavior. In particular, we show that most attractors are periodic in multistable systems, meaning that chaotic attractors are rare in such systems. After arguing that multistable systems have the general traits expected from a complex system, we pass to control them. Our controlling complexity ideas allow for both the stabilization and destabilization of any one of the coexisting states. The control of complexity differs from the standard control of chaos approach, an approach that makes use of the unstable periodic orbits embedded in an extended chaotic attractor. (c) 1997 American Institute of Physics.     

Observation and destruction of an elusive adsorbate with STM: O₂/TiO₂(110)

When a slightly defective rutile TiO?(110) surface is exposed to O?at elevated temperatures, the molecule dissociates at defects, filling O vacancies (V(O)) and creating O adatoms (O(ad)) on Ti(5c) rows. The adsorption of molecular O? at low temperatures has remained controversial. Low-temperature scanning tunneling microscopy of O?, dosed on TiO?(110) at a sample temperature of ≈100 K and imaged at 17 K, shows a molecular precursor at V(O) as a faint change in contrast. The adsorbed O? easily dissociates during the STM measurements, and the formation of O(ad)'s at both sides of the original V(O) is observed.     

Growth of one-dimensional Pd nanowires on the terraces of a reduced SnO2(101) surface

Palladium, vapor-deposited at room temperature on a reduced SnO2(101) surface, forms one-dimensional islands, one atomic layer high, 5 A wide, and up to 350 A long. Scanning tunneling microscopy shows that neighboring islands do not merge. First-principles calculations reveal the atomistic processes that lead to this, for metal oxide substrates unusual, overlayer growth. Formation of 1D islands is mediated by a large anisotropy in surface diffusion, strong Pd-Sn interaction, and the lack of stable binding sites at the sides of the Pd islands. Nucleation is defect mediated, and the initial nucleation site determines the width of the resulting nanocluster.     

Greedy sums of distinct squares

When a positive integer is expressed as a sum of squares, with each successive summand as large as possible, the summands decrease rapidly in size until the very end, where one may find two 's, or several 's. We find that the set of integers for which the summands are distinct does not have a natural density but that the counting function oscillates in a predictable way.

     

Formaldehyde Formation on Vanadium Oxide Surfaces V2O3(0001) and V2O5(001): How does the Stable Methoxy Intermediate Form?

Hydroxy‐mediated methoxy formation or stabilization is probably an important process in many methanol adsorption systems. Hydrogen atoms originating from the scission of the methanol O? H bond react with the substrate and form water. This process may result 1) in the production of additional surface defects as reactive centers for methoxy formation and 2) in the stabilization of methoxy groups by suppression of methanol formation.

     

Picosecond multidimensional fluorescence spectroscopy: a tool to measure real-time protein dynamics during function

Advanced multidimensional time-correlated single photon counting (mdTCSPC) and picosecond time-resolved fluorescence in combination with site-directed fluorescence labeling are valuable tools to study the properties of membrane protein surface segments on the pico- to nanoseconds time scale. Time-resolved fluorescence anisotropy changes of protein bound fluorescent probes reveal changes in protein dynamics and steric restriction. In addition, the change in fluorescence lifetime and intensity of the covalently bound fluorescent dye is indicative of environmental changes at the protein surface. In this study, we have measured the changes in fluorescence lifetime traces of the fluorescent dye fluorescein covalently bound to the first cytoplasmic loop of bacteriorhodopsin (bR) after light activation of protein function. The fluorescence is excited by a picosecond laser pulse. The retinylidene chromophore of bR is light-activated by a 10 ns laser pulse, which in turn triggers recording of a sequence of fluorescence lifetime traces in the mdTCSPC-module. The fluorescence decay changes upon protein function occur predominantly in the 100 ps time range. The kinetics of these changes shows two transitions between three intermediate states in the second part of the bR photocycle. Correlation with photocycle kinetics allows for the determination of reaction intermediates at the proteins surface which are coupled to changes in the retinal binding pocket.     

Configurational Isomerism in Polyoxovanadates

A water‐soluble derivative of the polyoxovanadate {V₁₅E₆O₄₂} (E=semimetal) archetype enables the study of cluster shell rearrangements driven by supramolecular interactions. A reaction unique to E=Sb, induced exclusively by ligand metathesis in peripheral [Ni(ethylenediamine)₃]²⁺ counterions, results in the formation of the metastable α₁* configurational isomer of the {V₁₄Sb₈O₄₂} cluster type. Contrary to all other polyoxovanadate shell architectures, this isomer comprises an inward‐oriented vanadyl group and is ca. 50 and 12 kJ mol^?1 higher in energy than the previously isolated α and β isomers, respectively. We discuss this unexpected reaction in light of supramolecular Sb?O???V and Sb?O???Sb contacts manifested in {V₁₄Sb₈O₄₂}₂ dimers detected in the solid state. ESI MS experiments confirm the stability of these dimers also in solution and in the gas phase. DFT calculations indicate that other, as of yet elusive isomers of {V₁₄Sb₈}, might be accessible as well.     

Kristallstruktur und Konformation eines linearen Pentapyrrols

The crystal structure of the pentapyrrin1 was determined by X-ray diffraction methodes at two temperatures (298K and 97K). It is the first structure determination of a linear polypyrrole with more than four pyrrole rings. In the crystal, the molecule is located on a crystallographic two-fold axis, which passes through the central pyrrole ring. It assumes a helical overall-conformation, which is stabilized by intramolecular hydrogen bonding. The acidic proton at the nitrogen atom of the central pyrrolic ring is disordered, being observed with half occupancy at two symmetry-equivalent positions off the crystallographic diad. Attempts to remove the disorder by cooling to 97K were unsuccessful, since no indication for a phase transition was detected.

     

Total harmonic distortion analysis for direct methanol fuel cell anode

In this study, total harmonic distortion (THD) analysis is put forward to illustrate nonlinear behavior of direct methanol fuel cell (DMFC) anode. THD simulations by means of different methanol oxidation kinetics as well as its experimental validation are both carried out. It is shown that the THD model adopting a three-step methanol oxidation mechanism with Kauranen–Frumkin/Temkin kinetics can be used to illustrate the THD variation for DMFC anode qualitatively. The experimental THD response at the frequency range from 0.063 Hz to 0.4 Hz is identified as the reflection of the nonlinearity variation of those kinetic steps involving intermediates in the methanol oxidation. In such a frequency domain, THD value decrease monotonously with decreasing methanol concentration, which notices its accessibility on methanol concentration detection.