Characterization of Interactions Involving Bromine in 2,2-Dibromo2,3-dihydroinden-1-one via Experimental Charge Density Analysis

Experimental and theoretical charge density analyses on 2,2-dibromo-2,3-dihydroinden-1-one have been carried out to quantify the topological features of a short CBr....O halogen bond with nearly linear geometry (2.922 angstrom, angle CBr....O = 172.7 degrees) and to assess the strength of the interactions using the topological features of the electron density. The electrostatic potential map indicates the presence of the s-hole on bromine, while the interaction energy is comparable to that of a moderate OH....O hydrogen bond. In addition, the energetic contribution of CH.....Br interaction is demonstrated to be on par with that of the CBr....O halogen bond in stabilizing the crystal structure.

``Conformational Simulation'' of Sulfamethizole by Molecular Complexation and Insights from Charge Density Analysis: Role of Intramolecular S center dot center dot center dot O Chalcogen Bonding

Intramolecular S center dot center dot center dot O chalcogen bonding and its potential to lock molecular conformation have been examined in the crystal forms of sulfamethizole, a sulfonamide antibiotic. Molecular complexes of sulfamethizole, including salts and cocrystal, have been synthesized, and their crystal structures were analyzed in order to examine the possible conformational preferences of the molecule in various ionic states and supramolecular environments (neutral/cocrystal, anionic salt, and cationic salt forms). The electrostatic potential mapped on Hirshfeld surfaces generated for these crystal forms provides insights into the possible binding modes of the drug in different environments. Further, the observed conformation locking feature has been rationalized in terms of the experimental charge density features of the intramolecular S center dot center dot O chalcogen bonding in sulfamethizole. The study quantitatively illustrates and rationalizes an intriguing case of a local minimum of molecular conformation being exclusively preferred over the global minimum, as it facilitates more efficient intermolecular interactions in a supramolecular environment.

Optoelectronic Properties of Graphene on Silicon Substrate: Effect of Defects in Graphene

Engineering of electronic energy band structure in graphene based nanostructures has several potential applications. Substrate induced bandgap opening in graphene results several optoelectronic properties due to the inter-band transitions. Various defects like structures, including Stone-Walls and higher-order defects are observed when a graphene sheet is exfoliated from graphite and in many other growth conditions. Existence of defect in graphene based nanostructures may cause changes in optoelectronic properties. Defect engineered graphene on silicon system are considered in this paper to study the tunability of optoelectronic properties. Graphene on silicon atomic system is equilibrated using molecular dynamics simulation scheme. Based on this study, we confirm the existence of a stable super-lattice. Density functional calculations are employed to determine the energy band structure for the super-lattice. Increase in the optical energy bandgap is observed with increasing of order of the complexity in the defect structure. Optical conductivity is computed as a function of incident electromagnetic energy which is also increasing with increase in the defect order. Tunability in optoelectronic properties will be useful in understanding graphene based design of photodetectors, photodiodes and tunnelling transistors.

The X-C---Y (X = O/F, Y = O, S, F, Cl, Br, N, P,) Carbon bond and hydrophobic interactions

While the tetrahedral face of methane has an electron rich centre and can act as a hydrogen bond acceptor, substitution of one of its hydrogens with some electron withdrawing group (such as -F/OH) can make the opposite face electron deficient. Electrostatic potential calculations confirm this and high level quantum calculations show interactions between the positive face of methanol/methyl fluoride and electron rich centers of other molecules such as H2O. Analysis of the wave functions of atoms in molecules shows the presence of an unusual C···Y interaction, which could be called 'carbon bonding'. NBO analysis and vibrational frequency shifts confirm the presence of this interaction. Given the properties of alkyl groups bonded to electronegative elements in biological molecules, such interactions could play a significant role, which is yet to be recognized. This and similar interactions could give an enthalpic contribution to what is called the 'hydrophobic interactions'.

S center dot center dot center dot O chalcogen bonding in sulfa drugs: insights from multipole charge density and X-ray wavefunction of acetazolamide

Experimental charge density analysis combined with the quantum crystallographic technique of X-ray wavefunction refinement (XWR) provides quantitative insights into the intra-and intermolecular interactions formed by acetazolamide, a diuretic drug. Firstly, the analysis of charge density topology at the intermolecular level shows the presence of exceptionally strong interaction motifs such as a DDAA-AADD (D-donor, A-acceptor) type quadruple hydrogen bond motif and a sulfonamide dimer synthon. The nature and strength of intra-molecular S center dot center dot center dot O chalcogen bonding have been characterized using descriptors from the multipole model (MM) and XWR. Although pure geometrical criteria suggest the possibility of two intra-molecular S center dot center dot center dot O chalcogen bonded ring motifs, only one of them satisfies the ``orbital geometry'' so as to exhibit an interaction in terms of an electron density bond path and a bond critical point. The presence of `s-holes' on the sulfur atom leading to the S center dot center dot center dot O chalcogen bond has been visualized on the electrostatic potential surface and Laplacian isosurfaces close to the `reactive surface'. The electron localizability indicator (ELI) and Roby bond orders derived from the `experimental wave function' provide insights into the nature of S center dot center dot center dot O chalcogen bonding.

The electronic, chemical and electrocatalytic processes and intermediates on iron oxide surfaces during photoelectrochemical water splitting

We re-assess experimental soft X-ray absorption spectra of the oxygen K-shell which we recorded operando from iron oxide during photoelectrochemical water splitting in KOH electrolyte. In particular, we refer to recently reported transitional electron hole states which originate within the charge carrier depletion layer of the iron oxide and on the iron oxide surface. For the latter we find that an intermediate oxy-peroxo species is formed on the iron oxide with increasing bias potential, which disappears upon further polarization of the electrode, concomitantly with the evolution and disappearance of the aforementioned surface state. The oxygen spectra contain also the spectroscopic signatures of the electrolyte water, the position of which changes with increasing bias potential towards lower X-ray energies, revealing the breaking and formation of hydrogen bonds in the water during the experiment. Combined with potential dependent impedance spectroscopy data we are able to sketch the molecular structure of chemical intermediates and their charge carrier dynamics. (C) 2015 Elsevier B.V. All rights reserved.

The effects of coil current distribution in a cylindrical electron-cyclotron-resonance reactor

Using a 2-D hybrid model, the authors have found that external currents play an important role in the plasma parameters in the reactor. The plasma density, temperature and electrostatic potential would be significantly influenced by the applied external currents.

Behavior of ar plasma formed in a high-density plasma source - an ecr reactor

In order to develop the ultra-large scale integration(ULSI), low pressure and high density plasma apparatus are required for etching and deposit of thin films. To understand critical parameters such as the pressure, temperature, electrostatic potential and energy distribution of ions impacting on the wafer, it is necessary to understand how these parameters are influenced by the power input and neutral gas pressure. In the present work, a 2-D hybrid electron fluid-particle ion model has been developed to simulate one of the high density plasma sources-an Electron Cyclotron Resonance (ECR) plasma system with various pressures and power inputs in a non-uniform magnetic field. By means of numerical simulation, the energy distributions of argon ion impacting on the wafer are obtained and the plasma density, electron temperature and plasma electrostatic potential are plotted in 3-D. It is concluded that the plasma density depends mainly on both the power input and neutral gas pressure. However, the plasma potential and electron temperature can hardly be affected by the power input, they seem to be primarily dependent on the neutral gas pressure. The comparison shows that the simulation results are qualitatively in good agreement with the experiment measurements.

甲烷团簇纯库仑爆炸的离子平均动能

利用一简单的经典静电模型研究了甲烷团簇纯库仑爆炸情况下产生的离子平均动能。研究表明，甲烷团簇爆炸后离子获得的平均动能和离子的初始平均静电势能的比值，与团簇的尺寸大小无关。这意味着在甲烷团簇纯库仑爆炸近似下，不必使用分子动力学模拟，离子获得的动能可以通过这一比值以及离子的初始静电势能进行估算。给出了不同碳离子价态下的离子平均动能和其初始平均静电势能的比值。

A variational framework for spectral discretization of the density matrix in Kohn Sham density functional theory

Kohn-Sham density functional theory (KSDFT) is currently the main work-horse of quantum mechanical calculations in physics, chemistry, and materials science. From a mechanical engineering perspective, we are interested in studying the role of defects in the mechanical properties in materials. In real materials, defects are typically found at very small concentrations e.g., vacancies occur at parts per million, dislocation density in metals ranges from $10^{10} m^{-2}$ to $10^{15} m^{-2}$, and grain sizes vary from nanometers to micrometers in polycrystalline materials, etc. In order to model materials at realistic defect concentrations using DFT, we would need to work with system sizes beyond millions of atoms. Due to the cubic-scaling computational cost with respect to the number of atoms in conventional DFT implementations, such system sizes are unreachable. Since the early 1990s, there has been a huge interest in developing DFT implementations that have linear-scaling computational cost. A promising approach to achieving linear-scaling cost is to approximate the density matrix in KSDFT. The focus of this thesis is to provide a firm mathematical framework to study the convergence of these approximations. We reformulate the Kohn-Sham density functional theory as a nested variational problem in the density matrix, the electrostatic potential, and a field dual to the electron density. The corresponding functional is linear in the density matrix and thus amenable to spectral representation. Based on this reformulation, we introduce a new approximation scheme, called spectral binning, which does not require smoothing of the occupancy function and thus applies at arbitrarily low temperatures. We proof convergence of the approximate solutions with respect to spectral binning and with respect to an additional spatial discretization of the domain. For a standard one-dimensional benchmark problem, we present numerical experiments for which spectral binning exhibits excellent convergence characteristics and outperforms other linear-scaling methods.

Detection of molecular interactions with modified ferrocene self-assembled monolayers.

Ferrocene-terminated self-assembled monolayers (Fc-SAMs) are one of the most studied molecular aggregates on metal electrodes. They are easy to fabricate and provide a stable and reproducible system to investigate the effect of the microenvironment on the electron transfer parameters. We propose a novel application for Fc-SAMs, the detection of molecular interactions, based on the modification of the SAM with target-specific receptors. Mixed SAMs were fabricated by coimmobilization on Au electrodes of thiolated alkane chains with three different head groups: hydroxy terminating head group, ferrocene head group, and a functional head group such as biotin. Upon binding, the intrinsic electric charge of the target (e.g., streptavidin) modifies the electrostatic potential at the plane of electron transfer, causing a shift in the formal potential E degrees '. The SAMs were characterized by AC voltammetry. The detection mechanism is confirmed by measurements of formal potential as a function of electrolyte pH.

Compact three-dimensional silicon termination solutions for high voltage SOI SuperJunction

This paper demonstrates and discusses novel "three dimensional" silicon based junction isolation/termination solutions suitable for high density ultra-low-resistance Lateral Super-Junction structures. The proposed designs are both compact and effective in safely distributing the electrostatic potential away from the active device area. The designs are based on the utilization of existing layers in the device fabrication line, hence resulting in no extra complexity or cost increase. The study/demonstration is done through extensive experimental measurements and numerical simulations. © 2012 IEEE.

Spintronics with graphene

Because of its fascinating electronic properties, graphene is expected to produce breakthroughs in many areas of nanoelectronics. For spintronics, its key advantage is the expected long spin lifetime, combined with its large electron velocity. In this article, we review recent theoretical and experimental results showing that graphene could be the long-awaited platform for spintronics. A critical parameter for both characterization and devices is the resistance of the contact between the electrodes and the graphene, which must be large enough to prevent quenching of the induced spin polarization but small enough to allow for the detection of this polarization. Spin diffusion lengths in the 100-μm range, much longer than those in conventional metals and semiconductors, have been observed. This could be a unique advantage for several concepts of spintronic devices, particularly for the implementation of complex architectures or logic circuits in which information is coded by pure spin currents. © Copyright 2012 Materials Research Society.

Control of a shock-wave/boundary-layer interaction and subsequent subsonic diffuser using a combination of vortex generators and bleed

An experimental investigation has been undertaken in which vortex generators (VGs) have been employed to inhibit boundary-layer separation produced by the combined adversepressure- gradient of a terminal shock-wave and subsonic diffuser. This setup has been developed as part of a program to produce a more inlet relevant flow-field using a small-scale wind tunnel than previous studies. The resulting flow is dominated by large-scale separation, and as such, is thought to be a good test-bed for flow control. In this investigation, VGs have been added to determine their potential for shock-induced separation mitigation. In line with previous studies, it was observed that the application of VGs alone was not able to significantly alleviate separation overall, because enlarged corner separations was observed. Only when control of the corner separations using corner bleed was employed alongside centre-span control using VGs was a significant improvement in both wall pressure recovery (6% increase) and stagnation pressure recovery (2.4% increase) observed. Copyright © 2012 by the American Institute of Aeronautics and Astronautics, Inc.

Electron tunneling through double magnetic barriers on the surface of a topological insulator

We study electron tunneling through a planar magnetic and electric barrier on the surface of a three-dimensional topological insulator. For the double barrier structures, we find (i) a directional-dependent tunneling which is sensitive to the magnetic field configuration and the electric gate voltage, (ii) a spin rotation controlled by the magnetic field and the gate voltage, (iii) many Fabry-Perot resonances in the transmission determined by the distance between the two barriers, and (iv) the electrostatic potential can enhance the difference in the transmission between the two magnetization configurations, and consequently lead to a giant magnetoresistance. Points (i), (iii), and (iv) are alike with that in graphene stemming from the same linear-dispersion relations.