Quantum chemical study on influence of intermolecular hydrogen bonding on the geometry, the atomic charges and the vibrational dynamics of 2,6-dichlorobenzonitrile

FT-IR (4000-400 cm(-1)) and FT-Raman (4000-200 cm(-1)) spectral measurements on solid 2,6-dichlorobenzonitrile (2,6-DCBN) have been done. The molecular geometry, harmonic vibrational frequencies and bonding features in the ground state have been calculated by density functional theory at the B3LYP/6-311++G (d,p) level. A comparison between the calculated and the experimental results covering the molecular structure has been made. The assignments of the fundamental vibrational modes have been done on the basis of the potential energy distribution (PED). To investigate the influence of intermolecular hydrogen bonding on the geometry, the charge distribution and the vibrational spectrum of 2,6-DCBN; calculations have been done for the monomer as well as the tetramer. The intermolecular interaction energies corrected for basis set superposition error (BSSE) have been calculated using counterpoise method. Based on these results, the correlations between the vibrational modes and the structure of the tetramer have been discussed. Molecular electrostatic potential (MEP) contour map has been plotted in order to predict how different geometries could interact. The Natural Bond Orbital (NBO) analysis has been done for the chemical interpretation of hyperconjugative interactions and electron density transfer between occupied (bonding or lone pair) orbitals to unoccupied (antibonding or Rydberg) orbitals. UV spectrum was measured in methanol solution. The energies and oscillator strengths were calculated by Time Dependent Density Functional Theory (TD-DFT) and matched to the experimental findings. TD-DFT method has also been used for theoretically studying the hydrogen bonding dynamics by monitoring the spectral shifts of some characteristic vibrational modes involved in the formation of hydrogen bonds in the ground and the first excited state. The C-13 nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the Gauge independent atomic orbital (GIAO) method and compared with experimental results. Standard thermodynamic functions have been obtained and changes in thermodynamic properties on going from monomer to tetramer have been presented. (C) 2013 Elsevier B.V. All rights reserved.

Digestive ripening facilitated atomic diffusion at nanosize regime: Case of AuIn2 and Ag3In intermetallic nanoparticles

Monodisperse colloidal gold-indium (AuIn2) intermetallic nanoparticles have been synthesized from Au and In colloids using the digestive ripening process. Formation of the intermetallic proceeds via digestive ripening facilitated atomic diffusion of Au and In atoms from the Au and In nanoparticles followed simultaneously by their growth in the solution. Optimization of the reaction temperature was found to be crucial for the formation of AuIn2 intermetallic from gold and indium nanoparticles. Transmission electron microscopy revealed the presence of nearly monodisperse nanoparticles of Au and AuIn2 with particle size distribution of 3.7 +/- 1.0 nm and 5.0 +/- 1.6 nm, respectively. UV-visible spectral studies brought out the absence of SPR band in pure AuIn2 intermetallic nanoparticles. Optical study and electron microscopy, in combination with powder X-ray diffraction established phase pure AuIn2 intermetallic nanoparticles unambiguously. The potential of such an unprecedented approach has been further exploited in the synthesis of Ag3In intermetallic nanoparticles with the dimension of less than 10 nm. (C) 2014 Elsevier B.V. All rights reserved.

Rainbow Emission from an Atomic Transition in Doped Quantum Dots

Although semiconductor quantum dots are promising materials for displays and lighting due to their tunable emissions, these materials also suffer from the serious disadvantage of self-absorption of emitted light. The reabsorption of emitted light is a serious loss mechanism in practical situations because most phosphors exhibit subunity quantum yields. Manganese-based phosphors that also exhibit high stability and quantum efficiency do not suffer from this problem but in turn lack emission tunability, seriously affecting their practical utility. Here, we present a class of manganese-doped quantum dot materials, where strain is used to tune the wavelength of the dopant emission, extending the otherwise limited emission tunability over the yellow-orange range for manganese ions to almost the entire visible spectrum covering all colors from blue to red. These new materials thus combine the advantages of both quantum dots and conventional doped phosphors, thereby opening new possibilities for a wide range of applications in the future.

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.

Quench dynamics and parity blocking in Majorana wires

We theoretically explore quench dynamics in a finite-sized topological fermionic p-wave superconducting wire with the goal of demonstrating that topological order can have marked effects on such non-equilibrium dynamics. In the case studied here, topological order is reflected in the presence of two (nearly) isolated Majorana fermionic end bound modes together forming an electronic state that can be occupied or not, leading to two (nearly) degenerate ground states characterized by fermion parity. Our study begins with a characterization of the static properties of the finite-sized wire, including the behavior of the Majorana end modes and the form of the tunnel coupling between them; a transfer matrix approach to analytically determine the locations of the zero energy contours where this coupling vanishes; and a Pfaffian approach to map the ground state parity in the associated phase diagram. We next study the quench dynamics resulting from initializing the system in a topological ground state and then dynamically tuning one of the parameters of the Hamiltonian. For this, we develop a dynamic quantum many-body technique that invokes a Wick's theorem for Majorana fermions, vastly reducing the numerical effort given the exponentially large Hilbert space. We investigate the salient and detailed features of two dynamic quantities-the overlap between the time-evolved state and the instantaneous ground state (adiabatic fidelity) and the residual energy. When the parity of the instantaneous ground state flips successively with time, we find that the time-evolved state can dramatically switch back and forth between this state and an excited state even when the quenching is very slow, a phenomenon that we term `parity blocking'. This parity blocking becomes prominently manifest as non-analytic jumps as a function of time in both dynamic quantities.

Magnetometry using Ramsey interferometry in a Yb atomic beam

We use the Ramsey separated oscillatory fields technique in a 400 degrees C thermal beam of ytterbium (Yb) atoms to measure the Larmor precession frequency (and hence the magnetic field) with high precision. For the experiment, we use the strongly allowed S-1(0) P-1(1) transition at 399 nm, and choose the odd isotope Yb-171 with nuclear spin I = 1/2, so that the ground state has only two magnetic sublevels m(F) = +/- 1/2. With a magnetic field of 22.2 G and a separation of about 400 mm between the oscillatory fields, the central Ramsey fringe is at 16.64 kHz and has a width of 350 Hz. The technique can be readily adapted to a cold atomic beam, which is expected to give more than an order-of-magnitude improvement in precision. The signal-to-noise ratio is comparable to other techniques of magnetometry; therefore it should be useful for all kinds of precision measurements such as searching for a permanent electric dipole moment in atoms.

Design and Evaluation of Torsional Probes for Multifrequency Atomic Force Microscopy

Multifrequency atomic force microscopy is a powerful nanoscale imaging and characterization technique that involves excitation of the atomic force microscope (AFM) probe and measurement of its response at multiple frequencies. This paper reports the design, fabrication, and evaluation of AFM probes with a specified set of torsional eigen-frequencies that facilitate enhancement of sensitivity in multifrequency AFM. A general approach is proposed to design the probes, which includes the design of their generic geometry, adoption of a simple lumped-parameter model, guidelines for determination of the initial dimensions, and an iterative scheme to obtain a probe with the specified eigen-frequencies. The proposed approach is employed to design a harmonic probe wherein the second and the third eigen-frequencies are the corresponding harmonics of the first eigen-frequency. The probe is subsequently fabricated and evaluated. The experimentally evaluated eigen-frequencies and associated mode shapes are shown to closely match the theoretical results. Finally, a simulation study is performed to demonstrate significant improvements in sensitivity to the second-and the third-harmonic spectral components of the tip-sample interaction force with the harmonic probe compared to that of a conventional probe.

Modification of metal-InGaAs Schottky barrier behaviour by atomic layer deposition of ultra-thin Al2O3 interlayers

The effect of inserting ultra-thin atomic layer deposited Al2O3 dielectric layers (1 nm and 2 nm thick) on the Schottky barrier behaviour for high (Pt) and low(Al) work function metals on n- and p-doped InGaAs substrates has been investigated. Rectifying behaviour was observed for the p-type substrates (both native oxide and sulphur passivated) for both the Al/p-InGaAs and Al/Al2O3/p-InGaAs contacts. The Pt contacts directly deposited on p-InGaAs displayed evidence of limited rectification which increased with Al2O3 interlayer thickness. Ohmic contacts were formed for both metals on n-InGaAs in the absence of an Al2O3 interlayer, regardless of surface passivation. However, limited rectifying behaviour was observed for both metals on the 2 nm Al2O3/n-InGaAs samples for the sulphur passivated InGaAs surface, indicating the importance of both surface passivation and the presence of an ultra-thin dielectric interlayer on the current-voltage characteristics displayed by these devices. (C) 2015 Elsevier B.V. All rights reserved.

Direct Measurement of Three-Dimensional Forces in Atomic Force Microscopy

Direct measurement of three-dimensional (3-D) forces between an atomic force microscope (AFM) probe and the sample benefits diverse applications of AFM, including force spectroscopy, nanometrology, and manipulation. This paper presents the design and evaluation of a measurement system, wherein the deflection of the AFM probe is obtained at two points to enable direct measurement of all the three components of 3-D tip-sample forces in real time. The optimal locations for measurement of deflection on the probe are derived for a conventional AFM probe. Further, a new optimal geometry is proposed for the probe that enables measurement of 3-D forces with identical sensitivity and nearly identical resolution along all three axes. Subsequently, the designed measurement system and the optimized AFM probe are both fabricated and evaluated. The evaluation demonstrates accurate measurement of tip-sample forces with minimal cross-sensitivities. Finally, the real-time measurement system is employed as part of a feedback control system to regulate the normal component of the interaction force, and to perform force-controlled scribing of a groove on the surface of polymethyl methacrylate.

Spotting 2D atomic layers on aluminum nitride thin films

Substrates for 2D materials are important for tailoring their fundamental properties and realizing device applications. Aluminum nitride (AIN) films on silicon are promising large-area substrates for such devices in view of their high surface phonon energies and reasonably large dielectric constants. In this paper epitaxial layers of AlN on 2 `' Si wafers have been investigated as a necessary first step to realize devices from exfoliated or transferred atomic layers. Significant thickness dependent contrast enhancements are both predicted and observed for monolayers of graphene and MoS2 on AlN films as compared to the conventional SiO2 films on silicon, with calculated contrast values approaching 100% for graphene on AlN as compared to 8% for SiO2 at normal incidences. Quantitative estimates of experimentally measured contrast using reflectance spectroscopy show very good agreement with calculated values. Transistors of monolayer graphene on AlN films are demonstrated, indicating the feasibility of complete device fabrication on the identified layers.

Quantitative characterization of adhesion and stiffness of corneal lens of Drosophila melanogaster using atomic force microscopy

Atomic force Microscopy (AFM) has become a versatile tool in biology due to its advantage of high-resolution imaging of biological samples close to their native condition. Apart from imaging, AFM can also measure the local mechanical properties of the surfaces. In this study, we explore the possibility of using AFM to quantify the rough eye phenotype of Drosophila melanogaster through mechanical properties. We have measured adhesion force, stiffness and elastic modulus of the corneal lens using AFM. Various parameters affecting these measurements like cantilever stiffness and tip geometry are systematically studied and the measurement procedures are standardized. Results show that the mean adhesion force of the ommatidial surface varies from 36 nN to 16 nN based on the location. The mean stiffness is 483 +/- 5 N/m, and the elastic modulus is 3.4 +/- 0.05 GPa (95% confidence level) at the center of ommatidia. These properties are found to be different in corneal lens of eye expressing human mutant tau gene (mutant). The adhesion force, stiffness and elastic modulus are decreased in the mutant. We conclude that the measurement of surface and mechanical properties of D. melanogaster using AFM can be used for quantitative evaluation of `rough eye' surface. (C) 2015 Elsevier Ltd. All rights reserved.

The Uniaxial Tensile Deformation of Ni Nanowire: Atomic-Scale Computer Simulations

The mechanical deformations of nickel nanowire subjected to uniaxial tensile strain at 300 K are simulated by using molecular dynamics with the quantum corrected Sutten-Chen many-body force field. We have used common neighbor analysis method to investigate the structural evolution of Ni nanowire during the elongation process. For the strain rate of 0.1%/ps, the elastic limit is up to about 11% strain with the yield stress of 8.6 GPa. At the elastic stage, the deformation is carried mainly through the uniform elongation of the distances between the layers (perpendicular to the Z-axis) while the atomic structure remains basically unchanged. With further strain, the slips in the {111} planes start to take place in order to accommodate the applied strain to carry the deformation partially, and subsequently the neck forms. The atomic rearrangements in the neck region result in a zigzag change in the stress-strain curve; the atomic structures beyond the region, however, have no significant changes. With the strain close to the point of the breaking, we observe the formation of a one-atom thick necklace in Ni nanowire. The strain rates have no significant effect on the deformation mechanism, but have some influence on the yield stress, the elastic limit, and the fracture strain of the nanowire.