Influence of chlorine substitution on the self-assembly of zinc phthalocyanine

The adsorption and ordering of zinc phthalocyanine (ZnPc) and octachloro zinc phthalocyanine (ZnPcCl(8)) on an Ag(111) surface is studied in situ by scanning tunneling microscopy under ultrahigh vacuum. Two-dimensional self-assembled supramolecular domains are observed for these two molecules. We show how substituting chlorine atoms for half of the peripheral hydrogen atoms on ZnPc influences the self-assembly mechanisms. While intermolecular interactions are dominated by van der Waals forces in ZnPc molecular networks, ZnPcCl(8) molecular packing undergoes a sequential phase evolution driven by the creation of C-Cl...H-C hydrogen bonds between adjacent molecules. At the end of this evolution, the final molecular assembly involves all possible hydrogen bonds. Our study also reveals the influence of molecule-substrate interactions through the presence of fault lines generating a stripe structure in the molecular film.     

Functional polymers: scanning force microscopy insights

Scanning force microscopy (SFM) and related techniques make it possible to visualize polymer systems with a molecular resolution. Beyond imaging, they also enable the unveiling of a variety of (dynamic) physico-chemical properties of both isolated polymer chains and their supramolecular architectures, including structural, mechanical and electronic properties. This article reviews recent progress in the use of SFM on polymers, with a particular emphasis on the mechanical properties of copolymers and single polymer chains, as well as on the bottom-up fabrication of supramolecular polymeric (helical) nanostructures in particular based upon pi-conjugated macromolecules as building blocks for nanoelectronics. Through a detailed understanding of the polymer behavior, we propose solutions for the generation of organic functional (nano)systems.     

Phase slip phenomena in superconductors: from ordered to chaotic dynamics

We consider flux penetration to a 2D superconducting cylinder. We show that in the low field limit the kinetics is deterministic. In the strong field limit the dynamics becomes stochastic. Surprisingly the inhomogeneity in the cylinder reduces the level of stochasticity because of the predominance of Kelvin-Helmholtz vortices.     

Interacting branching process as a simple model of innovation

We describe innovation in terms of a generalized branching process. Each new invention pairs with any existing one to produce a number of offspring, which is Poisson distributed with mean p. Existing inventions die with probability p/τ at each generation. In contrast with mean field results, no phase transition occurs; the chance for survival is finite for all p > 0. For τ = ∞, surviving processes exhibit a bottleneck before exploding superexponentially-a growth consistent with a law of accelerating returns. This behavior persists for finite τ. We analyze, in detail, the asymptotic behavior as p→0.     

Semidefinite and linear programming integrality gaps for scheduling identical machines

Sherali and Adams (SIAM J Discrete Math 3:411–430, 1990) and Lovász and Schrijver (SIAM J Optim 1:166–190, 1991) developed systematic procedures to construct the hierarchies of relaxations known as lift-and-project methods. They have been proven to be a strong tool for developing approximation algorithms, matching the best relaxations known for problems like Max-Cut and Sparsest-Cut. In this work we provide lower bounds for these hierarchies when applied over the configuration LP for the problem of scheduling identical machines to minimize the makespan. First we show that the configuration LP has an integrality gap of at least 1024/1023 by providing a family of instances with 15 different job sizes. Then we show that for any integer n there is an instance with n jobs in this family such that after \(\varOmega (n)\) rounds of the Sherali–Adams (\(\text {SA}\)) or the Lovász–Schrijver (\(\text {LS}_+\)) hierarchy the integrality gap remains at least 1024/1023.     

The semi-classical limit of large fermionic systems

We study a system of N fermions in the regime where the intensity of the interaction scales as 1 / N and with an effective semi-classical parameter \(\hbar =N^{-1/d}\) where d is the space dimension. For a large class of interaction potentials and of external electromagnetic fields, we prove the convergence to the Thomas–Fermi minimizers in the limit \(N\rightarrow \infty \). The limit is expressed using many-particle coherent states and Wigner functions. The method of proof is based on a fermionic de Finetti–Hewitt–Savage theorem in phase space and on a careful analysis of the possible lack of compactness at infinity.     

Reduced Dynamics of the Non-holonomic Whipple Bicycle

Though the bicycle is a familiar object of everyday life, modeling its full nonlinear three-dimensional dynamics in a closed symbolic form is a difficult issue for classical mechanics. In this article, we address this issue without resorting to the usual simplifications on the bicycle kinematics nor its dynamics. To derive this model, we use a general reduction-based approach in the principal fiber bundle of configurations of the three-dimensional bicycle. This includes a geometrically exact model of the contacts between the wheels and the ground, the explicit calculation of the kernel of constraints, along with the dynamics of the system free of any external forces, and its projection onto the kernel of admissible velocities. The approach takes benefits of the intrinsic formulation of geometric mechanics. Along the path toward the final equations, we show that the exact model of the bicycle dynamics requires to cope with a set of non-symmetric constraints with respect to the structural group of its configuration fiber bundle. The final reduced dynamics are simulated on several examples representative of the bicycle. As expected the constraints imposed by the ground contacts, as well as the energy conservation, are satisfied, while the dynamics can be numerically integrated in real time.     

Guest-host colloid crystals: experimental study and simulations

Disorder in colloid crystals was induced by doping them with a different number of large or small guest particles, which had a different deviation in size from the host colloids. The change in optical properties of the guest-host colloid crystals was assessed by using optical transmission spectroscopy while the variation in crystal structure was examined using scanning electron microscopy (SEM). The disruption in the crystalline lattices depended on the relative deviation in sizes of the guest and host particles and the concentration of the guest colloids. In parallel with experiments, the packing of spheres in guest-host crystals was modeled with a simulated annealing algorithm. A good correlation was found between the changes in crystal structure observed by SEM imaging and the simulated sphere packing. The experimental and simulated changes in the transmission spectra of guest-host colloid crystals were in good agreement.     

A model for the analysis of enthalpies and entropies of liquid binary alloys

The automatic treatment of calculations of chemical equilibrium in homogeneous phases requires analytical representation of the enthalpies and entropies of mixing of the components; therefore various approaches have been investigated, including in particular an attempt to find significant models. The ‘surrounded atom’ model provides a satisfactory method of representing all the thermodynamic characteristics of mixing in binary alloys, on the basis of four adjustable parameters.     

Monotone corrections for generic cell-centered finite volume approximations of anisotropic diffusion equations

We present a nonlinear technique to correct a general finite volume scheme for anisotropic diffusion problems, which provides a discrete maximum principle. We point out general properties satisfied by many finite volume schemes and prove the proposed corrections also preserve these properties. We then study two specific corrections proving, under numerical assumptions, that the corresponding approximate solutions converge to the continuous one as the size of the mesh tends to zero. Finally we present numerical results showing that these corrections suppress local minima produced by the original finite volume scheme.