A Molecular Dynamics Study of Atomic Correlations in Glassy BzS3t

Glassy B&, the parent compound of the superionic conductor LiI-Li&B& has been studied by the molecular dynamics technique using a new potential model. The results suggest that the glass is made up of local units of four-membered B2S2 rings bridged by sulfur atoms, leading to a chainlike structure. Various pair correlation functions have been analyzed, and the B2Sz rings have been found to be planar. The calculated neutron structure factor shows a peak at 1.4 A-' which has been attributed to B-B correlations at 5.6 A. The glass transition temperature of the simulated system has been calculated to be around 800 K.

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.

Amorphous W-S-N thin films: The atomic structure behind ultra-low friction

Amorphous W-S-N in the form of thin films has been identified experimentally as an ultra-low friction material, enabling easy sliding by the formation of a WS2 tribofilm. However, the atomic-level structure and bonding arrangements in amorphous W-S-N, which give such optimum conditions for WS2 formation and ultra-low friction, are not known. In this study, amorphous thin films with up to 37 at.% N are deposited, and experimental as well as state-of-the-art ab initio techniques are employed to reveal the complex structure of W-S-N at the atomic level. Excellent agreement between experimental and calculated coordination numbers and bond distances is demonstrated. Furthermore, the simulated structures are found to contain N bonded in molecular form, i.e. N-2, which is experimentally confirmed by near edge X-ray absorption fine structure and X-ray photoelectron spectroscopy analysis. Such N-2 units are located in cages in the material, where they are coordinated mainly by S atoms. Thus this ultra-low friction material is shown to be a complex amorphous network of W, S and N atoms, with easy access to W and S for continuous formation of WS2 in the contact region, and with the possibility of swift removal of excess nitrogen present as N-2 molecules. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A New Class Of Photo-Cross-Linkable Side-Chain Liquid Crystalline Polymers Containing Bis(Benzylidene)Cyclohexanone Units

This paper reports a new class of photo-cross-linkable side chain liquid crystalline polymers (PSCLCPs) based on the bis(benzylidene)cyclohexanone unit, which functions as both a mesogen and a photoactive center. Polymers with the bis(benzylidene)cyclohexanone unit and varying spacer length have been synthesized. Copolymers of bis(benzylidene)cyclohexanone containing monomer and cholesterol benzoate containing monomer with different compositions have also been prepared. All these polymers have been structurally characterized by spectroscopic techniques. Thermal transitions were studied by DSC, and mesophases were identified by polarized light optical microscopy (POM). The intermediate compounds OH-x, the monomers SCLCM-x, and the corresponding polymers PSCLCP-x, which are essentially based on bis(benzylidene)cyclohexanone, all show a nematic mesophase. Transition temperatures were observed to decrease with increasing spacer length. The copolymers with varying compositions exhibit a cholesteric mesophase, and the transition temperatures increase with the cholesteric benzoate units in the copolymer. Photolysis of the low molecular weight liquid crystalline bis(benzylidene)-cyclohexanone compound reveals that there are two kinds of photoreactions in these systems: the EZ photoisomerization and 2 pi + 2 pi addition. The EZ photoisomerization in the LC phase disrupts the parallel stacking of the mesogens, resulting in the transition from the LC phase to the isotropic phase. The photoreaction involving the 2 pi + 2 pi addition of the bis(benzylidene)cyclohexanone units in the polymer results in the cross-linking of the chains. The liquid crystalline induced circular dichroism (LCICD) studies of the cholesterol benzoate copolymers revealed that the cholesteric supramolecular order remains even after the photo-cross-linking.

A simulation study of the mixing, atomic flow and velocity profiles of crystalline materials during sliding

Self-contained Non-Equilibrium Molecular Dynamics (NEMD) simulations using Lennard-Jones potentials were performed to identify the origin and mechanisms of atomic scale interfacial behavior between sliding metals. The mixing sequence and velocity profiles were compared via MD simulations for three cases, viz.: sell-mated, similar and hard-softvcrystal pairs. The results showed shear instability, atomic scale mixing, and generation of eddies at the sliding interface. Vorticity at the interface suggests that atomic flow during sliding is similar to fluid flow under Kelvin-Helmholtz instability and this is supported by velocity profiles from the simulations. The initial step-function velocity profile spreads during sliding. However the velocity profile does not change much at later stages of the simulation and it eventually stops spreading. The steady state friction coefficient during simulation was monitored as a function of sliding velocity. Frictional behavior can be explained on the basis of plastic deformation and adiabatic effects. The mixing layer growth kinetics was also investigated.

Nature of dependence of spin-orbit splittings on atomic number

It has been shown that Dirac equation employing a constant value of the screening constant Z0 does not explain the variation of spin-orbit splittings of 2p and 3p levels with atomic number Z. A model which takes into account the variation of Z0 withZ is shown to satisfactorily predict the dependence of spinorbit splittings onZ.

An explanation for the rare occurrence of cis peptide units in proteins and polypeptides

The rarity of occurrence of cis peptide units is only partially explained by the higher intrinsic energy of the cis over the trans form, which provides a probability of 0·01 for cis peptide units to occur. An additional factor is the conformational restriction imposed by the occurrence of a cis peptide unit in a chain of trans units. Taking a section of three peptide units having the sequences trans-trans-trans (ttt) and trans-cis-trans (tct), conformational energy calculations indicate that the latter can occur only to an extent of 0·1%, unless there occurs the sequence X-Pro, in which case it is of the order of 30%. This explains the extreme rarity of cis peptide units, in general; however, it follows that even with non-prolyl residues, cis peptide units are not forbidden, but can occur in some rare examples and should be looked for.

Crystal state conformation of three model monomer units for the beta-bend ribbon structure

The molecular and crystal structures of three compounds, representing the repeating units of the -bend ribbon (an approximate 310-helix, with an intramolecular hydrogen-bonding donor every two residues), have been determined by x-ray diffraction. They are Boc-Aib-Hib-NHBzl, Z-Aib-Hib-NHBzl, and Z-L-Hyp-Aib-NHMe (Aib, -aminoisobutyric acid; Bzl, benzyl; Boc, t-butyloxycarbonyl; Hyp, hydroxyproline Hib, -hydroxyisobutyric acid; Z, benzyloxycarbonyl). The two former compounds are folded in a -bend conformation: type III (III) for Boc-Aib-Hib-NHBzl, while type II (II) for the Z analogue. Conversely, the structure of Z-L-Hyp-Aib-NHMe, although not far from a type II -bend, is partially open.

X-ray photoelectron spectroscopic studies on Se/As2S3 and Sb/As2S3 nanomultilayered film

Photoinduced diffusion in Se/As2S3 and Sb/As2S3 nanomultilayered thin films are studied by X-ray photoelectron spectroscopy (XPS). The XPS measurements show the atomic movements during photoinduced diffusion in Se/As2S3 and Sb/As2S3 nanomultilayered film. The analysis of experimental data describes the nature of light induced changes indifferent structural units. (C) 2009 Elsevier B.V. All rights reserved.

Ellipsometric study of Atomic Layer Deposited TiO2 thin films

Atomic layer deposition was used to obtain TiO2 thin films on Si (100) and fused quartz, using a novel metal organic precursor. The films were grown at 400 degrees C, varying the amount of oxygen used as the reactive gas. X-ray diffraction showed the films to be crystalline, with a mixture of anatase and rutile phases. To investigate their optical properties, ellipsometric measurements were made in the UV-Vis-NIR range (300-1700 nm). Spectral distribution of various optical constants like refractive index (n), absorption index (k), transmittance (T), reflectance (R), absorption (A) were calculated by employing Bruggemann's effective medium approximation (BEMA) and Maxwell-Garnet effective medium approximation, in conjunction with the Cauchy and Forouhi-Bloomer (FB) dispersion relations. A layered optical model has been proposed which gives the thickness, elemental and molecular composition, amorphicity and roughness (morphology) of the TiO2 film surface and and the film/substrate interface, as a function of oxygen flow rate The spectral distribution of the optical band gap (E-g(opt)), complex dielectric constants (epsilon' and epsilon''), and optical conductivity (sigma(opt)), has also been determined.

Cu-II-Azide Polymers of Cu-3 and Cu-6 Building Units: Synthesis,Structures, and Magnetic Exchange Mechanism

Two new neutral copper-azido polymers [Cu-3(N-3)(6)(tmen)(2)](n)(1)and [Cu-6(N-3)(12)(deen)(2)](n) (2) [tmen = N,N,N, N-tetramethylethylenediamine and deen = N,N-diethylethylenediamine] have been synthesized by using lower molar equivalents of the chelating diamine ligands with Cu(NO3)(2)center dot 3H(2)O and an excess of NaN3. The single crystal X-ray structure shows that in the basic unit of the 1D complex 1, the three Cu-II ions are linked by double end-on azido bridges with Cu-N-EO-Cu angles on both sides of the magnetic exchange critical angle of 108 degrees. Complex 2 is a 3D framework of a basic u-6 cluster. Cryomagnetic susceptibility measurements over a wide range of temperature exhibit dominant ferromagnetic behavior in both the complexes. Density functional theory calculations (B3LYP functional) have been performed on the trinuclear unit to provide a qualitative theoretical interpretation of the overall ferromagnetic behavior shown by the complex 1.

The composition dependence of electrical switching behavior of Ge7Se93-xSbx glasses

Bulk Ge7Se93-xSbx (21 <= x <= 32) glasses are prepared by melt quenching method and electrical switching studies have been undertaken on these samples to elucidate the type of switching and the composition and thickness dependence of switching voltages. On the basis of the compressibility and atomic radii, it has been previously observed that Se-based glasses exhibit memory switching behavior. However, the present results indicate that Ge7Se93-xSbx glasses exhibit threshold type electrical switching with high switching voltages. Further, these samples are found to show fluctuations in the current-voltage (I-V) characteristics. The observed threshold behavior of Ge7Se93-xSbx glasses has been understood on the basis of larger atomic radii and lesser compressibilities of Sb and Ge. Further. the high switching voltages and fluctuations in the I-V characteristics of Ge-Se-Sb samples can be attributed to the high resistance of the samples and the difference in thermal conductivities of different structural units constituting the local structure of these glasses. The switching voltages of Ge7Se93-xSbx glasses have been found to decrease with the increase in the Sb concentration. The observed composition dependence of switching voltages has been understood on the basis of higher metallicity of the Sb additive and also in the light of the Chemically Ordered Network (CON) model. Further, the thickness dependence of switching voltages has been studied to reassert the mechanism of switching.

[B4O9H2] Cyclic Borate Units as the Building Unit in a Family of Zinc Borate Structures

A solvothermal reaction of ZnO, boric acid (B(OH)(3)), and aliphatic airlines in a water-pyridine mixture gave four zinc borate phases of different dimensionalities: [Zn(B4O8H2)(C3H10N2)], I (one-dimensional); [Zn(B4O8H2)(C3H10N2)] H2O, II (two-dimensional); [Zn(B5O10H3)(C10H24N4)]center dot H2O, III (two-dimensional): and [Zn-2(B8O15H2)(C3H10N2)(2)], IV (three-dimensional). The structures are formed by the connectivity involving polyborate chains and layers with Zn2+ species. In all the compounds, the amine molecules act its file ligand binding either the same or different zn centers. The formation of two different structures, II and IV, from the same amine by varying the reaction time is noteworthy. Transformation studies on II indicate that the formation of IV. from II, is facile and has been investigated for the first time. Two of file compounds, I and III, exhibit activity for second-order nonlinear optical behavior. The UV exposure of the sample indicates the absorption of all the UV radiation suggesting that the zinc borate compounds could be exploited for UV-blocking applications. The compounds have been characterized by powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, UV-vis, photoluminescence, and NMR studies.

Nano-meter scale plasticity in KBr studied by nanoindenter and force microscopy

The early stages of plasticity in KBr single crystals have been studied by means of nano-meter-scale indentation in complementary experiments using both a nanoindenter and an atomic force microscope. Nanoindentafion experiments precisely correlate indentation depth and forces, while force microscopy provides high-resolution force measurements and images of the surface revealing dislocation activity. The two methods provide very similar results for the onset of plasticity in KBr. Upon loading we observe yield of the surface in atomic layer units which we attribute to the nucleation of single dislocations. Unloading is accompanied by plastic recovery as evident from a non-linear force distance unloading curve and delayed discrete plasticity events.

Anion directed template synthesis of Cu(II) complexes of a N,N,O donor mono-condensed Schiff base ligand: A molecular scaffold forming highly ordered H-bonded rectangular grids

Anion directed, template syntheses of two dinuclear copper(II) complexes of mono-condensed Schiff base ligand Hdipn (4-[(3-aminopentylimino)-methyl]-benzene-1,3-diol) involving 2,4- dihydroxybenzaldehyde and 1,3-diaminopentane were realized in the presence of bridging azide and acetate anions. Both complexes, [Cu-2(dipn)(2)(N-3)(2)] (1) and [Cu-2(dip(n))(2)(OAc)(2)] (2) have been characterized by X-ray crystallography. The two mononuclear units are joined together by basal-apical, double end-on azido bridges in complex 1 and by basal-apical, double mono-atomic acetate oxygen-bridges in 2. Both complexes form rectangular grid-like supramolecular structures via H-bonds connecting the azide or acetate anion and the p-hydroxy group of 2,4- dihydroxybenzaldehyde. Variable-temperature (300-2 K) magnetic susceptibility measurements reveal that complex 1 has antiferromagnetic coupling (J = -2.10 cm (1)) through the azide bridge while 2 has intra-dimer ferromagnetic coupling through the acetate bridge and inter-dimer antiferromagnetic coupling through H-bonds (J = 2.85 cm (1), J' = -1.08 cm (1)). (C) 2009 Elsevier B. V. All rights reserved.