Reversible Anion‐Driven Switching of an Organic 2D Crystal at a Solid–Liquid Interface

Ionic self‐assembly of charged molecular building blocks relies on the interplay between long‐range electrostatic forces and short‐range, often cooperative, supramolecular interactions, yet has been seldom studied in two dimensions at the solid–liquid interface. Here, we demonstrate anion‐driven switching of two‐dimensional (2D) crystal structure at the Au(111)/octanoic acid interface. Using scanning tunneling microscopy (STM), three organic salts with identical polyaromatic cation (PQPC₆⁺) but different anions (perchlorate, anthraquinonedisulfonate, benzenesulfonate) are shown to form distinct, highly ordered self‐assembled structures. Reversible switching of the supramolecular arrangement is demonstrated by in situ exchange of the anion on the pre‐formed adlayer, by changing the concentration ratio between the incoming and outgoing anion. Density functional theory (DFT) calculations reveal that perchlorate is highly mobile in the adlayer, and corroborate why this anion is only resolved transiently in STM. Surprisingly, the templating effect of the anion persists even where it does not become part of the adlayer 2D fabric, which we ascribe to differences in stabilization of cation conformations by the anion. Our results provide important insight into the structuring of mixed anion–cation adlayers. This is essential in the design of tectons for ionic self‐assembled superstructures and biomimetic adaptive materials and valuable also to understand adsorbate–adsorbate interactions in heterogeneous catalysis.     

Probabilistic calibration of discrete element simulations using the sequential quasi-Monte Carlo filter

The calibration of discrete element method (DEM) simulations is typically accomplished in a trial-and-error manner. It generally lacks objectivity and is filled with uncertainties. To deal with these issues, the sequential quasi-Monte Carlo (SQMC) filter is employed as a novel approach to calibrating the DEM models of granular materials. Within the sequential Bayesian framework, the posterior probability density functions (PDFs) of micromechanical parameters, conditioned to the experimentally obtained stress–strain behavior of granular soils, are approximated by independent model trajectories. In this work, two different contact laws are employed in DEM simulations and a granular soil specimen is modeled as polydisperse packing using various numbers of spherical grains. Knowing the evolution of physical states of the material, the proposed probabilistic calibration method can recursively update the posterior PDFs in a five-dimensional parameter space based on the Bayes’ rule. Both the identified parameters and posterior PDFs are analyzed to understand the effect of grain configuration and loading conditions. Numerical predictions using parameter sets with the highest posterior probabilities agree well with the experimental results. The advantage of the SQMC filter lies in the estimation of posterior PDFs, from which the robustness of the selected contact laws, the uncertainties of the micromechanical parameters and their interactions are all analyzed. The micro–macro correlations, which are byproducts of the probabilistic calibration, are extracted to provide insights into the multiscale mechanics of dense granular materials.     

Discrete modeling of sand–tire mixture considering grain-scale deformability

Mixing sand or soil with small pieces of tire is common practice in civil engineering applications. Although the properties of the soil are changed, it is environmentally friendly and sometimes economical. Nevertheless, the mechanical behavior of such mixtures is still not fully understood and more numerical investigations are required. This paper presents a novel approach for the modeling of sand–tire mixtures based on the discrete element method. The sand grains are represented by rigid agglomerates whereas the tire grains are represented by deformable agglomerates. The approach considers both grain shape and deformability. The micromechanical parameters of the contact law are calibrated based on experimental results from the literature. The effects of tire content and confining pressure on the stress–strain response are investigated in detail by performing numerical triaxial compression tests. The main results indicate that both strength and stiffness of the samples decrease with increasing tire content. A tire contact of 40% is identified as the boundary between rubber-like and sand-like behavior.     

Modification of Iron with Degradable Silver Phases Processed via Laser Beam Melting for Implants with Adapted Degradation Rate

In medical technology, implants are used to improve the quality of patients’ lives. The development of materials with adapted properties can further increase the benefit of implants. If implants are only needed temporarily, biodegradable materials are beneficial. In this context, iron-based materials are promising due to their biocompatibility and mechanical properties, but the degradation rate needs to be accelerated. Apart from alloying, the creation of noble phases to cause anodic dissolution of the iron-based matrix is promising. Due to its high electrochemical potential, immiscibility with iron, biocompatibility, and antibacterial properties, silver is suited for the creation of such phases. A suitable technology for processing immiscible material combinations is powder-bed-based procedure like laser beam melting. This procedure offers short exposure times to high temperatures and therefore a limited time for diffusion of alloying elements. As the silver phases remain after the dissolution of the iron matrix, a modification is needed to ensure their degradability. Following this strategy, pure iron with 5 wt% of a degradable silver–calcium–lanthanum alloy is processed via laser beam melting. Investigation of the microstructure yields achievement of the intended microstructure and long-term degradation tests indicates an impact on the degradation, but no increased degradation rate.     

Enterprise networks: The re-engineering of complex software systems

Today technology design can no longer be understood as a design process on a green site. Design and implementation of new technology are always dependent on existing technology and the way it is used by people. In this respect Software-Engineering has also changed to the characteristics of normal technology design taking into account existing computer systems. Experiences show that the conditions and needs of such Software-Reengineering projects are highly complex and differ in their special characteristics ranging from aspects of quality of existing system documentation to organizational structures of the computer departments concerned. The Task-Artifact Cycle presented here gives a suitable reengineering approach emphasizing both analysis and design in Software-Reengineering.     

Mixtures of (N2)1−x : (O2) x at High Pressures and Low Temperatures

We performed Raman measurements at 18 K and pressures up to 25 GPa in order to construct a tentative phase diagram of the (N ₂)_1–x :(O ₂)_x –system at low temperatures. We varied the composition of the mixed system over the whole concentration range. Here we focused on the systems with high nitrogen concentration and pressures above 2 GPa. It is known that at room temperature oxygen is highly solvable in the –phase of N ₂. The experimental results show that oxygen suppresses the disorder–order transition –N ₂.     

A new Fortran 90 program to compute regular and irregular associated Legendre functions

We present a modern Fortran 90 code to compute the regular and irregular associated Legendre functions for all x∈(−1,+1) (on the cut) and |x|>1 and integer degree (l) and order (m). The code applies either forward or backward recursion in (l) and (m) in the stable direction, starting with analytically known values for forward recursion and considering both a Wronskian based and a modified Miller's method for backward recursion. While some Fortran 77 codes existed for computing the functions off the cut, no Fortran 90 code was available for accurately computing the functions for all real values of x different from x=±1 where the irregular functions are not defined.

Program summary

Program title: Associated Legendre FunctionsCatalogue identifier: AEHE_v1_0Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEHE_v1_0.htmlProgram obtainable from: CPC Program Library, Queen's University, Belfast, N. IrelandLicensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.htmlNo. of lines in distributed program, including test data, etc.: 6722No. of bytes in distributed program, including test data, etc.: 310 210Distribution format: tar.gzProgramming language: Fortran 90Computer: Linux systemsOperating system: LinuxRAM: bytesClassification: 4.7Nature of problem: Compute the regular and irregular associated Legendre functions for integer values of the degree and order and for all real arguments. The computation of the interaction of two electrons, 1/|r₁−r₂|, in prolate spheroidal coordinates is used as one example where these functions are required for all values of the argument and we are able to easily compare the series expansion in associated Legendre functions and the exact value.Solution method: The code evaluates the regular and irregular associated Legendre functions using forward recursion when |x|<1 starting the recursion with the analytically known values of the first two members of the sequence. For values of the argument |x|<1, the upward recursion over the degree for the regular functions is numerically stable. For the irregular functions, backward recursion must be applied and a suitable method of starting the recursion is required. The program has two options; a modified version of Miller's algorithm and the use of the Wronskian relation between the regular and irregular functions, which was the method considered in [1]. Both approaches require the computation of a continued fraction to begin the recursion. The Wronskian method (which can also be described as a modified Miller's method) is a convenient method of computations when both the regular and irregular functions are needed.Running time: The example tests provided take a few seconds to run.References:

• [1] 

  A. Gil, J. Segura, A code to evaluate prolate and oblate spheroidal harmonics, Comput. Phys. Commun. 108 (1998) 267–278.