Two-dimensional Arrangement Research Articles

Chiral Discrete and Polymeric Uranyl Ion Complexes with (1 R,3 S)-(+)-Camphorate Ligands: Counterion-Dependent Formation of a Hexanuclear Cage.

Reaction of (1 R,3 S)-(+)-camphoric acid (H2cam) with uranyl ions under solvo-hydrothermal conditions and in the presence of bulky countercations gave five chiral complexes of varying dimensionality. [Cu( R,S-Me6cyclam)][UO2(Hcam)2(HCOO)2] (1) and [Ni( R,S-Me6cyclam)][UO2(cam)(HCOO)2] (2), in which the formate coligand is formed in situ, involve very similar countercations, but 1 is a discrete, mononuclear complex, whereas 2 crystallizes as a one-dimensional (1D) coordination polymer, and NH-bond donation by the macrocyclic ligand of the countercation complexes is present in both. [Co(en)3][(UO2)4(cam)( R,R-tart)2(OH)]·3H2O (3), in which en is ethylenediamine and H4 R,R-tart is R,R-tartaric acid, contains three enantiomerically pure chiral species, and it displays a two-dimensional (2D) arrangement, with the countercation again involved in NH-bond donation. While [PPh4][UO2(cam)(NO3)] (4) is a 1D polymer, [PPh3Me]3[NH4]3[(UO2)6(cam)9] (5) is a discrete, homochiral, and homoleptic hexanuclear cage with C3 point symmetry and a trigonal prismatic arrangement of the uranium atoms. This cage differs from the octanuclear, pseudocubic uranyl camphorate species previously described, thus providing an example of modulation of the cage size through variation of the structure-directing counterions. The cage in 5 is closely associated with three PPh3Me+ cations, two of them outside and with their methyl group directed toward the prism basis center, and one inside the cage cavity. While complex 5 is nonluminescent, complexes 1 and 4 have emission spectra in the solid state typical of equatorially hexacoordinated uranyl complexes. Solid-state photoluminescence quantum yields of 2 and 23% have been measured for complexes 1 and 4, respectively.

Resonant Plasmon-Enhanced Upconversion in Monolayers of Core-Shell Nanocrystals: Role of Shell Thickness.

The upconversion luminescence (UCL) of colloidal lanthanide-doped upconversion nanocrystals (UCNCs) can be improved either by precise encapsulation of the surface by optically inert shells around the core, by an alteration of the nearby environment via metal nanoparticles, or by a combination of both. Considering their potential importance in crystalline silicon photovoltaics, the present study investigates both effects for two-dimensional arrangements of UCNCs. Using excitation light of 1500 nm wavelength, we study the variation in the upconversion luminescence from an Er3+-doped NaYF4 core as a function of the thickness of a NaLuF4 shell in colloidal solutions as well as in spin-cast-assisted self-assembled monolayers of UCNCs. The observed UCL yields and decay times of Er3+ ions of the UCNCs increase with increasing shell thickness in both cases, and nearly no variation in decay times is observed in the transition of the UCNCs from solution to film configurations. The luminescence efficiency of the UCNC monolayers is further enhanced by electron-beam-lithographic-designed Au nanodiscs deposited either on top of or buried within the monolayer. It is observed that the improvement by the nanocrystal shells is greater than that of the Au nanodiscs.

Enhanced diffraction efficiency of two-dimensional phase gratings.

Phase gratings are used as beam multiplexers in the submillimeter and Terahertz spectral range. Two-dimensional beam arrangements can often be obtained most easily by the superposition of two one-dimensional grating structures. We show that in general this approach does not yield the maximum grating efficiency and propose a method to obtain significantly higher efficiencies for this grating class.

Supramolecular interaction-induced assemblies of polyanions and 2-aminopyridinium in two polyoxometalate-based hybrids.

Organic-inorganic hybrids consisting of organic cations and polyanions are promising functional materials due to their various compositions and structures. An important aspect of these materials is the interactions between the organic and inorganic components, which not only produce the final structures, but also influence the properties. Here, we investigated the interactions between organic cations and polyanions using protonated 2-aminopyridinium (Hap) as the cation, and successfully obtained two polyoxometalate-based hybrids, namely (C5H7N2)4[Mo8O26], (I), and (C5H7N2)2[NiMo6O16(OH)2{CH3C(CH2O)3}2]·4H2O, (II). In the crystal structure of (I), every Hap cation links with two polyanions by donating one or two N-H...O hydrogen bonds, and every polyanion is surrounded by eight Hap cations via terminal or bridging O atoms. Conversely, in compound (II), every Hap cation only links with one polyanion decorated by a triol ligand; this organic-inorganic component further assembles via uncoordinated water molecules. In the extended structures, Hap plays a key role, not only providing a counter charge, but also acting as `glue' linking polyanions in the role of hydrogen-bond donors. In both compounds, as the nodes of the supramolecular network, the polyanions exhibit an ordered two-dimensional arrangement due to strong hydrogen bonds and electrostatic interactions between the organic and inorganic parts. The electrochemistry of compound (I) shows that redox sourcing from polyanions is a surface-controlled process. Conversely, the magnetic behaviour of compound (II) indicates dominant antiferromagnetic properties.

Hybrid method of plane-wave and cylindrical-wave expansions for distributed Bragg-reflector pillars: formalism and its application to topological photonics

A hybrid computational method of plane-wave and cylindrical-wave expansions for distributed Bragg-reflector (DBR) pillars is proposed. The plane-wave expansion is employed to represent the one-dimensional periodic structure of the DBR. The cylindrical-wave expansion is employed to describe the scattering by circular pillars with the DBR structure inside. This formalism enables us to calculate the radiation fields, $t$-matrices, scattering cross sections, photonic band structures, and quality factors of the DBR pillars. Furthermore, optical properties of arrayed DBR pillars are also investigated with the aid of the multiple-scattering method. Using this formalism, we demonstrate explicitly that high $Q$ photonic band modes including the so-called bound states in continuum are obtained both in isolated and arrayed DBR pillars. We also present a novel formation of gapless Dirac-cone surface states in a three-dimensional photonic crystal composed of a two-dimensional periodic arrangement of core-shell DBR pillars.

Data Publics: Urban Protest, Analytics and the Courts

Data Publics: Urban Protest, Analytics and the Courts

CFD Analysis of Urban Canopy Flows Employing the V2F Model: Impact of Different Aspect Ratios and Relative Heights

Computational fluid dynamics (CFD) is currently used in the environmental field to simulate flow and dispersion of pollutants around buildings. However, the closure assumptions of the turbulence usually employed in CFD codes are not always physically based and adequate for all the flow regimes relating to practical applications. The starting point of this work is the performance assessment of the V2F (i.e.,v2¯ − f) model implemented in Ansys Fluent for simulating the flow field in an idealized array of two-dimensional canyons. The V2F model has been used in the past to predict low-speed and wall-bounded flows, but it has never been used to simulate airflows in urban street canyons. The numerical results are validated against experimental data collected in the water channel and compared with other turbulence models incorporated in Ansys Fluent (i.e., variations of bothk-εandk-ωmodels and the Reynolds stress model). The results show that the V2F model provides the best prediction of the flow field for two flow regimes commonly found in urban canopies. The V2F model is also employed to quantify the air-exchange rate (ACH) for a series of two-dimensional building arrangements, such as step-up and step-down configurations, having different aspect ratios and relative heights of the buildings. The results show a clear dependence of the ACH on the latter two parameters and highlight the role played by the turbulence in the exchange of air mass, particularly important for the step-down configurations, when the ventilation associated with the mean flow is generally poor.

Assembly of Hollow Carbon Nanospheres on Graphene Nanosheets and Creation of Iron-Nitrogen-Doped Porous Carbon for Oxygen Reduction.

Triblock copolymer micelles coated with melamine-formaldehyde resin were self-assembled into closely packed two-dimensional (2D) arrangements on the surface of graphene oxide sheets. Carbonizing these structures created a 2D architecture composed of reduced graphene oxide (rGO) sandwiched between two monolayers of sub-40 nm diameter hollow nitrogen-doped carbon nanospheres (N-HCNS). Electrochemical tests showed that these hybrid structures had better performance for oxygen reduction compared to physically mixed rGO and N-HCNS that were not chemically bonded together. Further impregnation of the sandwich structures with iron (Fe) species followed by carbonization yielded Fe1.6-N-HCNS/rGO-900 with a high specific surface area (968.3 m2 g-1), a high nitrogen doping (6.5 at%), and uniformly distributed Fe dopant (1.6 wt %). X-ray absorption fine structure analyses showed that most of the Fe in the nitrogen-doped carbon framework is composed of single Fe atoms each coordinated to four N atoms. The best Fe1.6-N-HCNS/rGO-900 catalyst performed better in electrocatalytic oxygen reduction than 20 wt % Pt/C catalyst in alkaline medium, with a more positive half-wave potential of 0.872 V and the same limiting current density. Bottom-up soft-patterning of regular carbon arrays on free-standing 2D surfaces should enable conductive carbon supports that boost the performance of electrocatalytic active sites.

Crystallization of supercooled liquid and amorphous silicene

Crystallization under isothermal condition of supercooled liquid and amorphous silicene (a-silicene) models has been studied via molecular dynamics (MD) simulation with Stillinger-Weber (SW) interaction potential. Supercooled liquid and a-silicene models containing 104 atoms are obtained via the rapid solidification process from the melt. At each given temperature below and above Tg, models are annealed from 5 ns up to 8 ns in order to investigate aging effect on two-dimensional structural arrangement of disordered Si-atoms. Time dependence of thermodynamic and structural quantities is analyzed including potential energy, radial distribution function (RDF), coordination number, buckling degree, ring and bond-angle distribution. We find that 2D-crystallization of supercooled liquid and a-silicene exhibits a first-order behavior. Time-temperature-transformation (TTT) diagram exhibits a commonly nose-shape by analyzing a wide temperature range from supercooled liquid to amorphous state. High critical cooling rates of a-silicene are found indicating low glass-formation ability of the system. Thermodynamic properties of crystallization of silicenes attained after-aging are studied in details and we clarify a novel scenario of crystallization. A homogenous tendency of natural quenched-in nucleation atoms aggregate into larger clusters in 2D Si supercooled liquid sheet. Consequently, a polycrystalline layer of silicene is developed with decent low-numbered chain defects as grain boundary. In contrast, crystallization of a-silicene shows a partial crystallization behavior: Crystal clusters are found to exhibit a heterogeneous growth in models obtained below Tg. Crystal formed from a-silicene is a quasi-equilibrium state with a large number of defects still existed in models after a long relaxing time.

Thermal Properties and Segmental Dynamics of Polymer Melt Chains Adsorbed on Solid Surfaces.

The glass transition of supported polystyrene (PS) and poly(2-vinylpyridine) (P2VP) thin films in the vicinity of the substrate interface was studied by using a nanoplasmonic sensing (NPS) method. This "nanocalorimetric" approach utilizes localized surface plasmon resonance from two-dimensional arrangements of sensor nanoparticles deposited on SiO2-coated glass substrates. The NPS results demonstrated the existence of a high glass transition temperature ( Tg,high) along with the bulk glass transition temperature ( Tg,bulk ≈ 100 °C for PS and P2VP) within the thin films: Tg,high ≈ 160 °C for PS and Tg,high ≈ 200 °C for P2VP. To understand the origin of the Tg,high, we also studied the thermal transitions of lone polymer chains strongly adsorbed onto the substrate surface using solvent rinsing. Interestingly, the NPS data indicated that the Tg,high is attributed to the adsorbed polymer chains. To provide a better understanding of the mechanism of the Tg,high, molecular dynamics simulations were performed on a PS film adsorbed on hydrophobic and hydrophilic substrates. The simulation results illuminated the presence of a higher density region closest to the substrate surface regardless of the magnitude of the polymer-solid interactions. We postulate that the highly packed chain conformation reduces the free volume at the substrate interface, resulting in the Tg,high. Moreover, the simulation results revealed that the deviation of the Tg,high from the bulk Tg,bulk becomes larger as the polymer-substrate interaction increases, which is in line with the experimental findings.

Children's Control/Display Stereotypes.

Objective The aim of this study was to determine control/display stereotypes for children of a range of ages and development of these stereotypes with age. Background Little is known about control/display stereotypes for children of different ages and the way in which these stereotypes develop with age. This study is part of a program to determine the need to design differentially for these age groups. Method We tested four groups of children with various tasks (age groups 5 to 7, 8 to 10, 11 to 13, 14 to 16), with about 30 in each group. Examples of common tasks were opening a bottle, turning on taps, and allocating numbers to keypads. More complex tasks involved rotating a control to move a display in a requested direction. Results Tasks with which different age groups were familiar showed no effect of age group. Different control/display arrangements generally showed an increase in stereotype strength with age, with dependence on the form of the control/display arrangement. Two-dimensional arrangements, with the control on the same plane as the display, had higher stereotype strength than three-dimensional arrangements for all age groups, suggesting an effect of familiarity with controls and displays with increasing age. Conclusion Children's control/display stereotypes do not differ greatly from those of adults, and hence, design for children older than 5 years of age, for control/display stereotypes, can be the same as that for adult populations. Application When designing devices for children, the relationship between controls and displays can be as for adult populations, for which there are considerable experimental data.

Potential dependent changes in the structural and dynamical properties of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide on graphite electrodes revealed by molecular dynamics simulations.

An understanding of the characteristics of ionic liquid/graphite interfaces is highly important for electrochemical devices such as batteries and capacitors. In this paper, we report microscopic studies of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMIM-TFSI) on charged graphite electrodes using molecular dynamics simulations to reveal the two-dimensional arrangement of the ions and their dynamics at the interfaces. Analyses of surface distribution and mobility of ions revealed that the ion arrangement changes from a bilayer type to a checkerboard type with increasing applied potential. Whereas the bilayer type arrangement increases the ionic mobility parallel to the interfaces with the negative potential, the ions arranged in the checkerboard type tend to localize because of the increased lateral electrostatic interactions. Furthermore, we revealed that the inhomogeneity of ionic distribution at the positive potential propagates up to a few nanometers from the interface.

High-resolution imaging of silicene on an Ag(111) surface by atomic force microscopy

Silicene, a two-dimensional (2D) honeycomb arrangement of Si atoms, is expected to have better electronic properties than graphene and has been mostly synthesized on Ag surfaces. Although scanning tunneling microscopy (STM) has been used for visualizing its atomic structure in real space, the interpretation of STM contrast is not straightforward and only the topmost Si atoms were observed on the $(4\ifmmode\times\else\texttimes\fi{}4)$ silicene/Ag(111) surface. Here, we demonstrate that high-resolution atomic force microscopy (AFM) can resolve all constituent Si atoms in the buckled honeycomb arrangement of the $(4\ifmmode\times\else\texttimes\fi{}4)$ silicene. Site-specific force spectroscopy attributes the origin of the high-resolution AFM images to chemical bonds between the AFM probe apex and the individual Si atoms on the $(4\ifmmode\times\else\texttimes\fi{}4)$ silicene. A detailed analysis of the geometric parameters suggests that the pulling up of lower-buckled Si atoms by the AFM tip could be a key for high-resolution AFM, implying a weakening of the Si-Ag interactions at the interface. We expect that high-resolution AFM will also unveil atomic structures of edges and defects of silicene, or other emerging 2D materials.

A broadband cross-polarization conversion anisotropic metasurface based on multiple plasmon resonances

A compact broadband cross-polarization conversion metasurface functioning in the microwave regime is realized and experimentally demonstrated. The metasurface consists of a two-dimensional periodic arrangement of anisotropic doubleslit split-ring-resonator-based unit cells printed on top of a dielectric substrate, backed by metallic cladding. The proposed metasurface converts an x- or y-polarized wave into its orthogonal polarization over a fractional bandwidth of 100% from 5– 15 GHz, both for normal as well as oblique incidence. Moreover, the sub-wavelength unit-cell size, thin dielectric substrate, and unique unit-cell design collectively make the response of the metasurface same for both polarizations and insensitive to the incidence angle. The designed structure is fabricated and tested. The measurement and simulation results are found to be consistent with each other.

Effective demagnetizing tensors in arrays of magnetic nanopillars

A model describing the effect of magnetic dipolar interactions on the susceptibility of magnetic nanopillars is presented. It is an extension of a recently reported model for three-dimensional randomlike dispersions of nearly spherical nanoparticles in equilibrium [S\'anchez et al., Phys. Rev. B 95, 134421 (2017)], to well-ordered arrays of nanoparticles out of equilibrium. To test it, a high-quality benchmark consisting of a two-dimensional hexagonal arrangement of quasi-identical parallel nickel nanopillars embedded in a porous alumina template was fabricated. This model is based on an effective demagnetizing tensor, which only depends on a few morphological parameters of the sample, as the nearest-neighbor distance between pillars and the volume fraction of pillars in the specimen. It allows us to obtain the nanopillar intrinsic susceptibility tensor from the magnetic response of the nanopillar ensemble. The values of the in-plane and normal-to-plane susceptibility of the sample are successfully predicted by the model. Furthermore, the model reproduces the susceptibility in the applied field direction, measured for different applied field angles. In this way, it provides a simple and accurate treatment to account for the complex magnetic effects produced by dipolar interactions.

Action at a distance in classical uniaxial ferromagnetic arrays.

We examine in detail the theoretical foundations of striking long-range couplings emerging in arrays of fluid cells connected by narrow channels by using a lattice gas (Ising model) description of a system. We present a reexamination of the well known exact determination of the two-point correlation function along the edge of a channel using the transfer matrix technique and a different interpretation is provided. The explicit form of the correlation length is found to grow exponentially with the cross section of the channels at the bulk two-phase coexistence. The aforementioned result is recaptured by a refined version of the Fisher-Privman theory of first order phase transitions in which the Boltzmann factor for a domain wall is decorated with a contribution stemming from the point tension originated at its end points. The Boltzmann factor for a domain wall together with the point tension is then identified exactly thanks to two independent analytical techniques, providing a critical test of the Fisher-Privman theory. We then illustrate how to build up the network model from its elementary constituents, the cells and the channels. Moreover, we are able to extract the strength of the coupling between cells and express them in terms of the length and width and coarse-grained quantities such as surface and point tensions. We then support our theoretical investigation with a series of corroborating results based on Monte Carlo simulations. We illustrate how the long-range ordering occurs and how the latter is signaled by the thermodynamic quantities corresponding to both planar and three-dimensional Ising arrays.

Emergence of Type-II Dirac Points in Graphynelike Photonic Lattices.

We theoretically demonstrate that a type-II class of tilted Dirac cones can emerge in generalized two-dimensional anisotropic lattice arrangements. This is achieved by introducing a special set of graphynelike exchange bonds by means of which the complete spectrum of the underlying Weyl Hamiltonian can be realized. Our abinitio calculations demonstrate a unique class of eigensolutions corresponding to a type-II class of Dirac fermionic excitations. Based on our approach, one can systematically synthesize a wide range of strongly anisotropic band diagrams having tilted Dirac cones with variable location and orientation. Moreover, we show that asymmetric conical diffraction, as well as edge states, can arise in these configurations. Our results can provide a versatile platform to observe, for the first time, optical transport around type-II Dirac points in two-dimensional optical settings under linear, nonlinear, and non-Hermitian conditions.

Electromagnetic field control with binary aperiodic nanostructures

Aperiodic, irregular structures offer a large number of degrees of freedom relative to periodic or quasi-periodic systems and hence the opportunity for more control over electromagnetic fields. The challenge is to understand the relation between structure and material and the possible response, as measured by achievable scattered field as a function of position and frequency. With this information, basic guidelines could become available to facilitate a computational design process. Having this goal in mind, near-field through far-field control is appraised through a multivariate statistical analysis of example binary two-dimensional nanostructured aperiodic material arrangements. The total variance and significant rank of the transmission matrix, equivalent to the field correlation at the detector plane in the situations treated, yields quantitative measures of the degree of control related to size, material properties, and material spatial decomposition. This analysis provides sensitivity information relevant for the realization of aperiodic structures that can control light as a function of position and frequency in new ways.

SYNTHESIS AND STRUCTURAL STUDY OF THE IONIC ENSEMBLE (RS)-NIPECOTIC ACID: OXALIC ACID: WATER

In this structure, an ionic ensemble assisted by hydrogen bonds, the molecules are connected by O--H···O and N--H···O hydrogen bonds, forming linearsemi-oxalate--semi-oxalate chains with intercalated R and S nipecotic molecules. The combination of these intermolecular interactions leads to the formation of a molecular assembly which can be described as a two-dimensional bilayer-like arrangement.

Space mapping optimisation of 2D array elements arrangement to reduce the radar cross‐scattering

The authors propose a novel aggressive space mapping (ASM) algorithm for the two-dimensional antenna array elements arrangement to reduce the antenna array radar cross-scattering; meanwhile, to ensure the radiation performance. The coarse model is evaluated with genetic algorithm and analytic formulations, the fine model verification is computed with the full wave method of moments (MoMs) enhanced by the equivalence principle algorithm (EPA). The high-order basis functions and matrix compression technique are employed in the EPA-MoM for further accelerations. Only small number of iterations in the ASM optimisation is required for the fine model verification, to achieve the optimisation requirements. Numerical tests of the horn antenna array optimisation with moderate time are presented to show the efficiency of the proposed algorithm.