Universal tight binding model for chemical reactions in solution and at surfaces. I. Organic molecules

As is now well established, a first order expansion of the Hohenberg-Kohn total energy density functional about a trial input density, namely, the Harris-Foulkes functional, can be used to rationalize a non self consistent tight binding model. If the expansion is taken to second order then the energy and electron density matrix need to be calculated self consistently and from this functional one can derive a charge self consistent tight binding theory. In this paper we have used this to describe a polarizable ion tight binding model which has the benefit of treating charge transfer in point multipoles. This admits a ready description of ionic polarizability and crystal field splitting. It is necessary in constructing such a model to find a number of parameters that mimic their more exact counterparts in the density functional theory. We describe in detail how this is done using a combination of intuition, exact analytical fitting, and a genetic optimization algorithm. Having obtained model parameters we show that this constitutes a transferable scheme that can be applied rather universally to small and medium sized organic molecules. We have shown that the model gives a good account of static structural and dynamic vibrational properties of a library of molecules, and finally we demonstrate the model's capability by showing a real time simulation of an enolization reaction in aqueous solution. In two subsequent papers, we show that the model is a great deal more general in that it will describe solvents and solid substrates and that therefore we have created a self consistent quantum mechanical scheme that may be applied to simulations in heterogeneous catalysis.

Spatially-resolved mapping of history-dependent coupled electrochemical and electronical behaviors of electroresistive NiO

Bias-induced oxygen ion dynamics underpins a broad spectrum of electroresistive and memristive phenomena in oxide materials. Although widely studied by device-level and local voltage-current spectroscopies, the relationship between electroresistive phenomena, local electrochemical behaviors, and microstructures remains elusive. Here, the interplay between history-dependent electronic transport and electrochemical phenomena in a NiO single crystalline thin film with a number of well-defined defect types is explored on the nanometer scale using an atomic force microscopy-based technique. A variety of electrochemically-active regions were observed and spatially resolved relationship between the electronic and electrochemical phenomena was revealed. The regions with pronounced electroresistive activity were further correlated with defects identified by scanning transmission electron microscopy. Using fully coupled mechanical-electrochemical modeling, we illustrate that the spatial distribution of strain plays an important role in electrochemical and electroresistive phenomena. These studies illustrate an approach for simultaneous mapping of the electronic and ionic transport on a single defective structure level such as dislocations or interfaces, and pave the way for creating libraries of defect-specific electrochemical responses.

On the Complexity of Universal Leader Election

Electing a leader is a fundamental task in distributed computing. In its implicit version, only the leader must know who is the elected leader. This article focuses on studying the message and time complexity of randomized implicit leader election in synchronous distributed networks. Surprisingly, the most "obvious" complexity bounds have not been proven for randomized algorithms. In particular, the seemingly obvious lower bounds of Ω(m) messages, where m is the number of edges in the network, and Ω(D) time, where D is the network diameter, are nontrivial to show for randomized (Monte Carlo) algorithms. (Recent results, showing that even Ω(n), where n is the number of nodes in the network, is not a lower bound on the messages in complete networks, make the above bounds somewhat less obvious). To the best of our knowledge, these basic lower bounds have not been established even for deterministic algorithms, except for the restricted case of comparison algorithms, where it was also required that nodes may not wake up spontaneously and that D and n were not known. We establish these fundamental lower bounds in this article for the general case, even for randomized Monte Carlo algorithms. Our lower bounds are universal in the sense that they hold for all universal algorithms (namely, algorithms that work for all graphs), apply to every D, m, and n, and hold even if D, m, and n are known, all the nodes wake up simultaneously, and the algorithms can make any use of node's identities. To show that these bounds are tight, we present an O(m) messages algorithm. An O(D) time leader election algorithm is known. A slight adaptation of our lower bound technique gives rise to an Ω(m) message lower bound for randomized broadcast algorithms. 

An interesting fundamental problem is whether both upper bounds (messages and time) can be reached simultaneously in the randomized setting for all graphs. The answer is known to be negative in the deterministic setting. We answer this problem partially by presenting a randomized algorithm that matches both complexities in some cases. This already separates (for some cases) randomized algorithms from deterministic ones. As first steps towards the general case, we present several universal leader election algorithms with bounds that tradeoff messages versus time. We view our results as a step towards understanding the complexity of universal leader election in distributed networks.

Microneedle characterisation: the need for universal acceptance criteria and GMP specifications when moving towards commercialisation

With interest in microneedles as a novel drug transdermal delivery system increasing rapidly since the late 1990s (Margetts and Sawyer Contin Educ Anaesthesia Crit Care Pain. 7(5):171-76, 2007), a diverse range of microneedle systems have been fabricated with varying designs and dimensions. However, there are still very few commercially available microneedle products. One major issue regarding microneedle manufacture on an industrial scale is the lack of specific quality standards for this novel dosage form in the context of Good Manufacturing Practice (GMP). A range of mechanical characterisation tests and microneedle insertion analysis techniques are used by researchers working on microneedle systems to assess the safety and performance profiles of their various designs. The lack of standardised tests and equipment used to demonstrate microneedle mechanical properties and insertion capability makes it difficult to directly compare the in use performance of candidate systems. This review highlights the mechanical tests and insertion analytical techniques used by various groups to characterise microneedles. This in turn exposes the urgent need for consistency across the range of microneedle systems in order to promote innovation and the successful commercialisation of microneedle products.

Lead-bismuth eutectic corrosion behaviors of ferritic/martensitic steels in low oxygen concentration environment

In order to investigate the compatibility of candidate structural materials with liquid metals, two kinds of ferritic/martensitic steels were chosen to contact with lead–bismuth eutectic in sealed quartz–glass tubes. The corrosion exposures were for 500 and 3000 h. Results showed that the oxidation layer and carbide dissolution layer on the two steels grew with contact time under oxygen unsaturated condition. Short-term corrosion behavior of a newly developed steel showed better lead–bismuth eutectic corrosion resistance than T91 at 873 K.

The United Kingdom, the United Nations Human Rights Council and the first cycle of the Universal Periodic Review

The introduction of the Universal Periodic Review (UPR) mechanism as an innovative component of the new Human Rights Council in 2006 has suffered little academic scrutiny. This is partly because it holds as its objective an improvement in human rights situations on the ground, a goal that is difficult to test amongst so many possible causal factors attributable to law reform and policy change, and partly due to the fact that the mechanism has only completed one full cycle of review. This article seeks to remedy this absence of analysis by examining the experience of the United Kingdom during its first review. In doing so, the article first considers the conception of the UPR, before progressing to examine the procedure and recommendations made to the UK by its peers. Finally, the article considers the five year review of the UPR which occurred as a subset of the Human Rights Council Review in 2011 and the resulting changes to the process modalities.

Reclaiming the Radical in Universal Human Rights: Universality as Universalisation

The universality of human rights has been a fiercely contested issue throughout their history. This article contributes to scholarly engagements with the universality of human rights by proposing a re-engagement with this concept in a way that is compatible with the aims of radical politics. Instead of a static attribute or characteristic of rights this article proposes that universality can be thought of as, drawing from Judith Butler, an ongoing process of universalisation. Universality accordingly emerges as a site of powerful contest between competing ideas of what human rights should mean, do or say, and universal concepts are continually reworked through political activity. This leads to a differing conception of rights politics than traditional liberal approaches but, moreover, challenges such approaches. This understanding of universality allows human rights to come into view as potentially of use in interrupting liberal regimes and, crucially, opens possibilities to reclaim the radical in rights.

Elastodynamic Modeling and Analysis for an Exechon Parallel Kinematic Machine

As a newly invented parallel kinematic machine (PKM), Exechon has attracted intensive attention from both academic and industrial fields due to its conceptual high performance. Nevertheless, the dynamic behaviors of Exechon PKM have not been thoroughly investigated because of its structural and kinematic complexities. To identify the dynamic characteristics of Exechon PKM, an elastodynamic model is proposed with the substructure synthesis technique in this paper. The Exechon PKM is divided into a moving platform subsystem, a fixed base subsystem and three limb subsystems according to its structural features. Differential equations of motion for the limb subsystem are derived through finite element (FE) formulations by modeling the complex limb structure as a spatial beam with corresponding geometric cross sections. Meanwhile, revolute, universal, and spherical joints are simplified into virtual lumped springs associated with equivalent stiffnesses and mass at their geometric centers. Differential equations of motion for the moving platform are derived with Newton's second law after treating the platform as a rigid body due to its comparatively high rigidity. After introducing the deformation compatibility conditions between the platform and the limbs, governing differential equations of motion for Exechon PKM are derived. The solution to characteristic equations leads to natural frequencies and corresponding modal shapes of the PKM at any typical configuration. In order to predict the dynamic behaviors in a quick manner, an algorithm is proposed to numerically compute the distributions of natural frequencies throughout the workspace. Simulation results reveal that the lower natural frequencies are strongly position-dependent and distributed axial-symmetrically due to the structure symmetry of the limbs. At the last stage, a parametric analysis is carried out to identify the effects of structural, dimensional, and stiffness parameters on the system's dynamic characteristics with the purpose of providing useful information for optimal design and performance improvement of the Exechon PKM. The elastodynamic modeling methodology and dynamic analysis procedure can be well extended to other overconstrained PKMs with minor modifications.

The Casimir effect in the presence of compactified universal extra dimensions

The Casimir force in a system consisting of two parallel conducting plates in the presence of compactified universal extra dimensions (UXD) is analyzed. The Casimir force with UXDs differs from the force obtained without extra dimensions. A new power law for the Casimir force is derived. By comparison to experimental data the size R of the universal extra dimensions can be restricted to R⩽10 nm for one extra dimension.

Effects of temperature and strain rate on the tensile behaviors of SIMP steel in static lead bismuth eutectic

In order to assess the susceptibility of candidate structural materials to liquid metal embrittlement, this work investigated the tensile behaviors of ferritic-martensitic steel in static lead bismuth eutectic (LBE). The tensile tests were carried out in static lead bismuth eutectic under different temperatures and strain rates. Pronounced liquid metal embrittlement phenomenon is observed between 200 °C and 450 °C. Total elongation is reduced greatly due to the liquid metal embrittlement in LBE environment. The range of ductility trough is larger under slow strain rate tensile (SSRT) test.