Spontaneous self-assembly of designed cyclic dipeptide (Phg-Phg) into two-dimensional nano- and mesosheets

In this study, we present the spontaneous self-assembly of designed simplest aromatic cyclic dipeptides of (L-Phg-L-Phg) and (D-Phg-L-Phg) to form highly stable two-dimensional (2D) nano- and mesosheets with large lateral surface area. Various microscopy data revealed that the morphology of 2D mesosheets resembles the hierarchical natural materials with layered structure. Solution and solid-state NMR studies on cyclo(L-Phg-L-Phg) revealed the presence of strong (N-H-O) hydrogen-bonded molecular chains supported by aromatic pi-pi interactions to form 2D mesosheets. Interestingly, cyclo(D-Phg-L-Phg) self-assembles to form single-crystalline as well as non-crystalline 2D rhomboid sheets with large lateral dimension. X-ray diffraction analysis revealed the stacking of (N-H-O) hydrogen-bonded molecular layers along c-axis supported by aromatic pi-pi interactions. The thermogravimetric analysis shows two transitions with overall high thermal stability attributed to layered hierarchy found in 2D mesosheets.

Anisotropy induced crossover from weakly to strongly first order melting of two dimensional solids

Melting and freezing transitions in two dimensional (2D) systems are known to show highly unusual characteristics. Most of the earlier studies considered atomic systems: the melting of 2D molecular solids is still largely unexplored. In order to understand the role of anisotropy as well as multiple energy and length scales present in molecular systems, here we report computer simulation studies of melting of 2D molecular systems. We computed a limited portion of the solid-liquid phase diagram. We find that the interplay between the strength of isotropic and anisotropic interactions can give rise to rich phase diagram consisting of isotropic liquid and two crystalline phases-honeycomb and oblique. The nature of the transition depends on the relative strength of the anisotropic interaction and a strongly first order melting turns into a weakly first order transition on increasing the strength of the isotropic interaction. This crossover can be attributed to an increase in stiffness of the solid phase free energy minimum on increasing the strength of the anisotropic interaction. The defects involved in melting of molecular systems are quite different from those known for the atomic systems.

Low-density three-dimensional foam using self-reinforced hybrid two-dimensional atomic layers

Low-density nanostructured foams are often limited in applications due to their low mechanical and thermal stabilities. Here we report an approach of building the structural units of three-dimensional (3D) foams using hybrid two-dimensional (2D) atomic layers made of stacked graphene oxide layers reinforced with conformal hexagonal boron nitride (h-BN) platelets. The ultra-low density (1/400 times density of graphite) 3D porous structures are scalably synthesized using solution processing method. A layered 3D foam structure forms due to presence of h-BN and significant improvements in the mechanical properties are observed for the hybrid foam structures, over a range of temperatures, compared with pristine graphene oxide or reduced graphene oxide foams. It is found that domains of h-BN layers on the graphene oxide framework help to reinforce the 2D structural units, providing the observed improvement in mechanical integrity of the 3D foam structure.

Laterally structured ripple and square phases with one and two dimensional thickness modulations in a model bilayer system

Molecular dynamics simulations of bilayers in a surfactant/co-surfactant/water system with explicit solvent molecules show formation of topologically distinct gel phases depending upon the bilayer composition. At low temperatures, the bilayers transform from the tilted gel phase, L beta', to the one dimensional (1D) rippled, P beta' phase as the surfactant concentration is increased. More interestingly, we observe a two dimensional (2D) square phase at higher surfactant concentration which, upon heating, transforms to the gel L beta' phase. The thickness modulations in the 1D rippled and square phases are asymmetric in two surfactant leaflets and the bilayer thickness varies by a factor of similar to 2 between maximum and minimum. The 1D ripple consists of a thinner interdigitated region of smaller extent alternating with a thicker non-interdigitated region. The 2D ripple phase is made up of two superimposed square lattices of maximum and minimum thicknesses with molecules of high tilt forming a square lattice translated from the lattice formed with the thickness minima. Using Voronoi diagrams we analyze the intricate interplay between the area-per-head-group, height modulations and chain tilt for the different ripple symmetries. Our simulations indicate that composition plays an important role in controlling the formation of low temperature gel phase symmetries and rippling accommodates the increased area-per-head-group of the surfactant molecules.

Reconstruction of Two-Dimensional Spectra from One-Dimensional Projections-Examples from Solid State NMR

The use of Projection Reconstruction (PR) to obtain two-dimensional (2D) spectra from one-dimensional (1D) data in the solid state is illustrated. The method exploits multiple 1D spectra obtained using magic angle spinning and off-magic angle spinning. The spectra recorded under the influence of scaled heteronuclear scalar and dipolar couplings in the presence of homonuclear dipolar decoupling sequences have been used to reconstruct J/D Resolved 2D-NMR spectra. The use of just two 1D spectra is observed sufficient to reconstruct a J-resolved 2D-spectrum while a Separated Local Field (SLF) 2D-NMR spectrum could be obtained from three 1D spectra. The experimental techniques for recording the 10 spectra and procedure of reconstruction are discussed and the reconstructed results are compared with 20 experiments recorded in traditional methods. The application of the technique has been made to a solid polycrystalline sample and to a uniaxially oriented liquid crystal. Implementation of PR-NMR in solid state provides high-resolution spectra as well as leads to significant reduction in experimental time. The experiments are relatively simple and are devoid of several technical complications involved in performing the 2D experiments.

New generation of two-dimensional spintronic systems realized by coupling of Rashba and Dirac fermions

Intriguing phenomena and novel physics predicted for two-dimensional (2D) systems formed by electrons in Dirac or Rashba states motivate an active search for new materials or combinations of the already revealed ones. Being very promising ingredients in themselves, interplaying Dirac and Rashba systems can provide a base for next generation of spintronics devices, to a considerable extent, by mixing their striking properties or by improving technically significant characteristics of each other. Here, we demonstrate that in BiTeI@PbSb2Te4 composed of a BiTeI trilayer on top of the topological insulator (TI) PbSb2Te4 weakly- and strongly-coupled Dirac-Rashba hybrid systems are realized. The coupling strength depends on both interface hexagonal stacking and trilayer-stacking order. The weakly-coupled system can serve as a prototype to examine, e.g., plasmonic excitations, frictional drag, spin-polarized transport, and charge-spin separation effect in multilayer helical metals. In the strongly-coupled regime, within similar to 100 meV energy interval of the bulk TI projected bandgap a helical state substituting for the TI surface state appears. This new state is characterized by a larger momentum, similar velocity, and strong localization within BiTeI. We anticipate that our findings pave the way for designing a new type of spintronics devices based on Rashba-Dirac coupled systems.

Tunable Rashba effect in two-dimensional LaOBiS2 films: Ultrathin candidates for spin field effect transistors

Rashba spin splitting is a two-dimensional (2D) relativistic effect closely related to spintronics. However, so far there is no pristine 2D material to exhibit enough Rashba splitting for the fabrication of ultrathin spintronic devices, such as spin field effect transistors (SFET). On the basis of first-principles calculations, we predict that the stable 2D LaOBiS2 with only 1 nm of thickness can produce remarkable Rashba spin splitting with a magnitude of 100 meV. Because the medium La2O2 layer produces a strong polar field and acts as a blocking barrier, two counter-helical Rashba spin polarizations are localized at different BiS 2 layers. The Rashba parameter can be effectively tuned by the intrinsic strain, while the bandgap and the helical direction of spin states sensitively depends on the external electric field. We propose an advanced Datta-Das SFET model that consists of dual gates and 2D LaOBiS2 channels by selecting different Rashba states to achieve the on-off switch via electric fields. © 2013 American Chemical Society.

Comparison of free spectral range and quality factor for two-dimensional square and circular microcavities

Free spectral range of whispering-gallery (WG)-like modes in a two-dimensional (2D) square microcavity is found to be twice that in a 2D circular microcavity. The quality factor of the WG-like mode with the low mode number in a 2D square microcavity, calculated by the finite-difference time-domain (FDTD) technique and the Pade approximation method, is found to exceed that of the WG mode in 2D circular microcavity with the same cavity dimension and close mode wavelength.

Mode softening in charge-density excitations of a two-dimensional electron gas driven by Rashba spin-orbit interaction

The electron density response of a uniform two-dimensional (2D) electron gas is investigated in the presence of a perpendicular magnetic field and Rashba spin-orbit interaction (SOI). It is found that, within the Hartree-Fock approximation, a charge density excitation mode below the cyclotron resonance frequency shows a mode softening behavior, when the spin-orbit coupling strength falls into a certain interval. This mode softening indicates that the ground state of an interacting uniform 2D electron gas may be driven by the Rashba SOI to undergo a phase transition to a nonuniform charge density wave state.

Binding energy of excitons bound to neutral donors in two-dimensional semiconductors

The binding energies of excitons bound to neutral donors in two-dimensional (2D) semiconductors within the spherical-effective-mass approximation, which are nondegenerate energy bands, have been calculated by a variational method for a relevant range of the effective electron-to-hole mass ratio sigma. The ratio of the binding energy of a 2D exciton bound to a neutral donor to that of a 2D neutral donor is found to be from 0.58 to 0.10. In the limit of vanishing sigma and large sigma, the results agree fairly well with previous experimental results. The results of this approach are compared with those of earlier theories.

Shubnikov de Haas oscillations of a two-dimensional electron gas in a modulation-doped Zn0.80Cd0.20Se/ZnS0.06Se0.94 single quantum well

The magnetotransport properties of the two-dimensional (2D) electron gas confined in a modulation-doped Zn0.80Cd0.20Se/ZnS0.06Se0.94 single quantum well structure were studied at temperatures down to 0.35 K in magnetic fields up to 7.5 T. Well resolved 2D Shubnikovde Haas (SdH) oscillations were observed, although the conductivity of the sample in the as grown state was dominated by a bulk parallel conduction layer. After removing most of the parallel conduction layer by wet chemical etching the amplitude and number of SdH oscillations increased. From the temperature dependence of the amplitude the effective mass of the electrons was estimated as 0.17 m(0). Copyright (C) 1996 Published by Elsevier Science Ltd

Self-assembly of ionic liquids-stabilized Pt nanoparticles into two-dimensional patterned nanostructures at the air-water interface

In this paper, we demonstrate the self-assembly of ionic liquids (ILs)-stabilized Pt nanoparticles into two-dimensional (2D) patterned nanostructures at the air-water interface under ambient conditions. Here, ILs are not used as solvents but as mediators by virtue of their pronounced self-organization ability in synthesis of self-assembled, highly organized hybrid Pt nanostructures. It is also found that the morphologies of the 2D patterned nanostructures are directly connected with the quantities of ILs. Due to the special structures of ILs-stabilized Pt nanoparticles, 2D patterned Pt nanostructures can be formed through the pi-pi stack interactions and hydrogen bonds. The resulting 2D patterned Pt nanostructures exhibit good electrocatalytic activity toward oxygen reduction.

Orientation, Flow, and Clogging in a Two-Dimensional Hopper: Ellipses vs. Disks

Two-dimensional (2D) hopper flow of disks has been extensively studied. Here, we investigate hopper flow of ellipses with aspect ratio $\alpha = 2$, and we contrast that behavior to the flow of disks. We use a quasi-2D hopper containing photoelastic particles to obtain stress/force information. We simultaneously measure the particle motion and stress. We determine several properties, including discharge rates, jamming probabilities, and the number of particles in clogging arches. For both particle types, the size of the opening, $D$, relative to the size of particles, $\ell$ is an important dimensionless measure. The orientation of the ellipses plays an important role in flow rheology and clogging. The alignment of contacting ellipses enhances the probability of forming stable arches. This study offers insight for applications involving the flow of granular materials consisting of ellipsoidal shapes, and possibly other non-spherical shapes.

Theory of enhanced magnetic anisotropy induced by Pt adatoms on two-dimensional Co clusters supported on a Pt(111) substrate

Calculations are reported of the magnetic anisotropy energy of two-dimensional (2D) Co nanostructures on a Pt(111) substrate. The perpendicular magnetic anisotropy (PMA) of the 2D Co clusters strongly depends on their size and shape, and rapidly decreases with increasing cluster size. The PMA calculated is in reasonable agreement with experimental results. The sensitivity of the results to the Co-Pt spacing at the interface is also investigated and, in particular, for a complete Co monolayer we note that the value of the spacing at the interface determines whether PMA or in-plane anisotropy occurs. We find that the PMA can be greatly enhanced by the addition of Pt adatoms to the top surface of the 2D Co clusters. A single Pt atom can induce in excess of 5 meV to the anisotropy energy of a cluster. In the absence of the Pt adatoms the PMA of the Co clusters falls below 1 meV/Co atom for clusters of about 10 atoms whereas, with Pt atoms added to the surface of the clusters, a PMA of 1 meV/Co atom can be maintained for clusters as large as about 40 atoms. The effect of placing Os atoms on the top of the Co clusters is also considered. The addition of 5d atoms and clusters on the top of ferromagnetic nanoparticles may provide an approach to tune the magnetic anisotropy and moment separately.

4,4 '-Dipyridyl-N,N '-dioxide complexes of metal-thiocyanate/selenocyanate: pi-stacked molecular rods as three-dimensional support for two-dimensional polymeric sheets and intra/interchain S center dot center dot center dot S interaction dependent architecture of the R-2(2)(8) synthon driven assembly of one-dimensional polymeric chains

Three supramolecular complexes of Co(II) using SCN-/SeCN- in combination with 4,4'-dipyridyl-N,N'-dioxide (dpyo), i.e., {[Co(SCN)(2)(dpyo)(2)].(dpyo)}(n) ( 1), {[Co(SCN)(2)(dpyo)(H2O)(2)].(H2O)}(n) ( 2), {[Co(SeCN)(2)(dpyo)(H2O)(2)]center dot(H2O)}(n) ( 3), have been synthesized and characterized by single-crystal X-ray analysis. Complex 1 is a rare example of a dpyo bridged two-dimensional (2D) coordination polymer, and pi-stacked dpyo supramolecular rods are generated by the lattice dpyo, passing through the rhombic grid of stacked layers, resulting in a three-dimensional (3D) superstructure. Complexes 2 and 3 are isomorphous one-dimensional (1D) coordination polymers [-Co-dpyo-Co-] that undergo self-assembly leading to a bilayer architecture derived through an R-2(2)(8) H-bonding synthon between coordinated water and dpyo oxygen. A reinvestigation of coordination polymers [Mn(SCN)(2)(dpyo)( H2O)(MeOH)](n) ( 4) and {[Fe(SCN)(2)(dpyo)(H2O)(2)]center dot(H2O)}(n) ( 5) reported recently by our group [ Manna et al. Indian J. Chem. 2006, 45A, 1813] reveals brick wall topology rather than bilayer architecture is due to the decisive role of S center dot center dot center dot S/Se center dot center dot center dot Se interactions in determining the helical nature in 4 and 5 as compared to zigzag polymeric chains in 2 and 3, although the same R-2(2)(8) synthon is responsible for supramolecular assembly in these complexes.