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The nanoscopic structure of biodegradable choline-based naphthenic acid ionic liquids near the hexagonal boron-nitride (h-BN) surface was analyzed using quantum mechanics calculations and molecular dynamics simulations. The effects of the type of the ring (aliphatic or aromatic) and the size of the ring in the anion counterpart of the aliphatic ionic liquids (ILs) on the configurations, binding energies, orbital energies, density of states, charge transfer, and thermochemistry of adsorption of ILs on the h-BN surface were investigated. Also the significance of non-covalent interactions on the adsorption of ILs was disclosed from the quantum theory of atoms in molecule. The results of radial distribution functions, number density, and also charge density profiles showed the existence of a solid-like bottom layer in the vicinity of the surface. Angular distribution functions revealed that while the most probable orientation in aromatic anions is parallel to the h-BN sheet, the most probable orientation in aliphatic rings apparently is perpendicular to the surface. The mobility of cations and anions in the studied ILs with respect to the h-BN sheet was analyzed using their mean square displacements. For all ions near the surface, dynamics in the parallel direction were faster than those in the z-direction due to the structuring of the solid-like layer of ILs near the h-BN surface. Altogether, this study provides new insights into the physisorption of this new class of biodegradable ILs on h-BN nanosheets at the molecular level. [ABSTRACT FROM AUTHOR]

The structural and dynamic properties of water molecules in a uniformly charged nanopore have been studied using the method of classical molecular dynamics simulation. When confined in an uncharged nanopore with an appropriate radius, water molecules are aligned along the nanopore axis and form a single-file structure with the dipole vectors pointing toward the same end of the nanopore. We demonstrate here that when the nanopore is uniformly charged, the water molecules in the nanopore pack more tightly and the water molecules near the two ends of the nanopore are no longer aligned along the nanopore axis but tend to be aligned perpendicularly to the nanopore axis. The water dipole vectors do not point toward the same nanopore end. When the nanopore is positively charged, the water molecules in the nanopore align with their oxygen atoms pointing to the center of the nanopore. The central water molecule forms an L-defect. However for a negatively charged nanopore, the water molecules in the nanopore take up the opposite orientation. A D-defect is formed at the center of the nanopore. Furthermore, the water molecules in the negatively charged nanopore with moderate atomic partial charges diffuse and transport more quickly than the water molecules in an uncharged nanopore. [ABSTRACT FROM AUTHOR]

“Charge inversion” is a phenomenon in which multivalent counterions overcompensate for interfacial charges and invert the sign of the net charge near a surface. This phenomenon is believed to be relevant to biologically important processes such as DNA condensation, and hence it has attracted much attention. We investigated the polar orientation of interfacial water molecules at two different negatively charged interfaces in the absence and presence of La3+ using heterodyne-detected vibrational sum frequency generation spectroscopy, which can directly determine the up/down orientation of interfacial molecules. It was found that the orientations of water molecules at a bio-relevant phospholipid interface change from the hydrogen-up to the hydrogen-down with the addition of 10 µM La3+. This change of water orientation indicates that the net charge at the phospholipid interface is inverted by adsorption of La3+ to the phosphate headgroup. By contrast, at an alkylsulfate interface, the majority of the interfacial water molecules remain hydrogen-up orientated even in the presence of 25 mM La3+, indicating that the sulfate headgroup is still solvated by up-oriented water. The observed headgroup specificity suggests that charge inversion at the phospholipid interface originates primarily from the chemical interaction between the phosphate and La3+ ion. [ABSTRACT FROM AUTHOR]

Understanding the interaction between hydrogen (H) and helium-vacancy (He-V) complexes in tungsten (W) is important for the development of plasma-facing materials in fusion reactors. H trapping by HexVy complexes in bulk W, as well as the H solution behavior and H trapping by HexV complexes near W(100), W(111), and W(110) surfaces, has been investigated by first-principles computer simulations using density function theory. The results show that the sequential H binding energies to HexV complexes in bulk W decrease with the increasing number of H and He. For the HexV2 complexes in bulk W, H prefers to trap at interstitial sites near the junction of the di-vacancy, where the H can minimize the isosurface of optimal charge density. The most stable interstitial sites for H below W surfaces are dependent on the surface orientation. Our calculations indicate that H atoms tend to prefer a depth of 0.3 nm below the W(100) and W(111) surfaces due to the surface reconstruction. The binding energy of H to a HeV complex near W surfaces has the most significant orientation dependence below the W(111) surface, followed by the W(100) and W(110) surfaces. Compared with the bulk value, the largest difference in the average binding energy of H to the stable HexV complexes at the three W surfaces is about 0.2 eV. Furthermore, the effect of surfaces on the H binding energy to HexV complexes can be ignored for depths greater than 0.65 nm. [ABSTRACT FROM AUTHOR]

Density function theory calculations have been performed to study the stability of small helium-vacancy (He-V) complexes near tungsten (W) surfaces of different orientations. The results show that the stability of vacancies and He-V complexes near W surfaces depends on surface orientation. However, as the depth below the surface increased beyond about 0.65–0.8 nm, the stability of He-V complexes is similar to the bulk. The formation energies of single vacancies and di-vacancies at depths less than 0.2 nm below the W(110) surface are higher than for W(100) or W(111) surfaces, but have lower energies at depths between 0.2 and 0.65 nm. The formation energies of He-V complexes below W surfaces are sensitive to the geometric orientation of the He and vacancy, especially below the W(111) surface. Within about 0.2 nm of the top layer of the three W surfaces, neither a vacancy nor a di-vacancy can trap He. Because of the lower formation energy of He-V complexes and higher He binding energy to vacancies below the W(110) surface, the He desorption from the W(110) surface is less likely to occur than from the W(100) and W(111) surfaces. Our results provide fundamental insight into the differences in surface morphology changes observed in single W crystals with different surface orientations under He plasma exposure. [ABSTRACT FROM AUTHOR]

Surprisingly long-ranged intermolecular correlations begin to appear in isotropic (orientationally disordered) phases of liquid crystal forming molecules when the temperature or density starts to close in on the boundary with the nematic (ordered) phase. Indeed, the presence of slowly relaxing, strongly orientationally correlated, sets of molecules under putatively disordered conditions (“pseudo-nematic domains”) has been apparent for some time from light-scattering and optical-Kerr experiments. Still, a fully microscopic characterization of these domains has been lacking. We illustrate in this paper how pseudo-nematic domains can be studied in even relatively small computer simulations by looking for order-parameter tensor fluctuations much larger than one would expect from random matrix theory. To develop this idea, we show that random matrix theory offers an exact description of how the probability distribution for liquid-crystal order parameter tensors converges to its macroscopic-system limit. We then illustrate how domain properties can be inferred from finite-size-induced deviations from these random matrix predictions. A straightforward generalization of time-independent random matrix theory also allows us to prove that the analogous random matrix predictions for the time dependence of the order-parameter tensor are similarly exact in the macroscopic limit, and that relaxation behavior of the domains can be seen in the breakdown of the finite-size scaling required by that random-matrix theory. [ABSTRACT FROM AUTHOR]

Structural and dynamical properties of interfacial water molecules near a hexagonal boron nitride sheet (h-BN) are investigated by means of Born-Oppenheimer molecular dynamics simulations. Orientational profiles in the interfacial regions reveal two distinct types of water molecules near the BN surface. Depending on the positions of the water molecules, on top of either N or B atoms, one type contains water molecules that are oriented with one OH bond pointing toward the N atoms and the other type contains water molecules that remain parallel to the BN sheet. Distinct hydrogen bonding and stabilization energies of these two types of water molecules are found from our calculations. In order to see the effects of dispersion interactions, simulations are performed with the BLYP (Becke-Lee-Yang-Parr) functional and also BLYP with Grimme's D3 corrections (BLYPD3). An enhancement of water ordering near the surface is observed with the inclusion of dispersion corrections. Further analysis of the diffusion coefficients, rotational time correlation functions, and hydrogen bond dynamics shows that water molecules near the h-BN sheet move faster compared to bulk water molecules both translationally and rotationally. The water molecules in the first layer are found to show substantial lateral diffusion. The escape dynamics of water from the solvation layer at the BN surface is also looked at in the current study. We have also investigated some of the electronic properties of interfacial water such as the charge density and dipole moment. It is found that the water molecules at the surface of the BN sheet have a lower dipole moment than bulk molecules. [ABSTRACT FROM AUTHOR]

An important initial step in the combustion of gasoline and diesel fuels is the abstraction of hydrogen from alkylbenzenes to form resonance-stabilized alkyl benzyl radicals. This work uses, for the first time, double resonance spectroscopy methods to explore the conformation-specific vibronic and infrared spectroscopy of the a-ethylbenzyl (αEtBz) and α-propylbenzyl (αPrBz) radicals. Local mode Hamiltonian modeling enables assignment of the alkyl CH stretch IR spectra, accounting for Fermi resonance that complicates aliphatic alkyl CH stretch IR spectroscopy. The ground state conformational preferences of the ethyl and propyl chains are changed from those in the alkylbenzenes themselves, with global minima occurring for an in-plane orientation of the alkyl chain (trans) about its first dihedral angle (Φƒ123, numbers are alkyl C atoms. C1 is CH radical site). This in-plane structure is the only observed conformer for the α-EtBz radical, while two conformers, tt and tg' share this orientation at the first dihedral, but differ in the second (Φ1234) for the αPrBz radical. The in-plane orientation lowers the local site frequencies of the CH2 group stretches immediately adjacent to the benzylic radical site by about 50 cm-1 relative to those in pure alkyl chains or alkylbenzenes. This effect of the radical site is localized on the first CH2 group, with little effect on subsequent members of the alkyl chain. In the D1 excited electronic state, an out-of-plane orientation is preferred for the alkyl chains, leading to torsional mode Franck-Condon activity in the D0-D1 spectra that is both conformer-specific and diagnostic of the conformational change. [ABSTRACT FROM AUTHOR]

A comprehensive understanding of chain-branching effects, essential for establishing general knowledge of the structure-property-phenomenon relationship in polymer science, has not yet been found, due to a critical lack of knowledge on the role of short-chain branches, the effects of which have mostly been neglected in favor of the standard entropic-based concepts of long polymers. Here, we show a significant effect of short-chain branching on the structural and dynamical properties of polymeric materials, and reveal the molecular origins behind the fundamental role of short branches, via atomistic nonequilibrium molecular dynamics and mesoscopic Brownian dynamics by systematically varying the strength of the mobility of short branches. We demonstrate that the fast random Brownian kinetics inherent to short branches plays a key role in governing the overall structure and dynamics of polymers, leading to a compact molecular structure and, under external fields, to a lesser degree of structural deformation of polymer, to a reduced shear-thinning behavior, and to a smaller elastic stress, compared with their linear analogues. Their fast dynamical nature being unaffected by practical flow fields owing to their very short characteristic time scale, short branches would substantially influence (i.e., facilitate) the overall relaxation behavior of polymeric materials under various flowing conditions. [ABSTRACT FROM AUTHOR]

Enhanced kinetic stability of vapor-deposited glasses has been established for a variety of glass organic formers. Several recent reports indicate that vapor-deposited glasses can be orientationally anisotropic. In this work, we present results of extensive molecular simulations that mimic a number of features of the experimental vapor deposition process. The simulations are performed on a generic coarse-grained model and an all-atom representation of N,N'-bis(3-methylphenyl)-N,N'- diphenylbenzidine (TPD), a small organic molecule whose vapor-deposited glasses exhibit considerable orientational anisotropy. The coarse-grained model adopted here is found to reproduce several key aspects reported in experiments. In particular, the molecular orientation of vapor-deposited glasses is observed to depend on substrate temperature during deposition. For a fixed deposition rate, the molecular orientation in the glasses changes from isotropic, at the glass transition temperature, Tg, to slightly normal to the substrate at temperatures just below Tg. Well below Tg, molecular orientation becomes predominantly parallel to the substrate. The all-atom model is used to confirm some of the equilibrium structural features of TPD interfaces that arise above the glass transition temperature. We discuss a mechanism based on distinct orientations observed at equilibrium near the surface of the film, which get trapped within the film during the non-equilibrium process of vapor deposition. [ABSTRACT FROM AUTHOR]

Previous methods for determining whether a uniform region of a sample is crystalline or isotropic-- what we call the "state of internal orientation" S--require a priori knowledge of properties of the purely crystalline and purely isotropic states. In addition, these methods can be ambiguous in their determination of state S for particular materials and, for a given material, the spectral methods can be ambiguous when using particular peaks. Using first-principles Raman theory, we have discovered a simple, non-resonance, polarized Raman method for determining the state S that requires no information a priori and will work unambiguously for any material using any vibrational mode. Similar to the concept behind "magic angle spinning" in NMR, we have found that for a special set of incident/analyzed polarizations and scattering angle, the dependence of the Raman modulation depth M on the sample composition--and, for crystalline regions, the unit cell orientation--falls out completely, leaving dependence on only whether the region is crystalline (M = 1) or isotropic (M = 0). Further, upon scanning between homogeneous regions or domains within a heterogeneous sample, our signal M is a clear detector of the region boundaries, so that when combined with methods for determining the orientations of the crystalline domains, our method can be used to completely characterize the molecular structure of an entire heterogeneous sample to a very high certainty. Interestingly, our method can also be used to determine when a given mode is vibrationally degenerate. While simulations on realistic terthiophene systems are included to illustrate our findings, our method should apply to any type of material, including thin films, molecular crystals, and semiconductors. Finally, our discovery of these relationships required derivations of Raman intensity formulas that are at least as general as any we have found, and herein we present our comprehensive formulas for both the crystalline and isotropic states. [ABSTRACT FROM AUTHOR]

Strong short-range intermolecular interactions result in position and orientation correlations between nearest neighbour molecules in isotropic liquids, but it is generally assumed that such correlations extend at most a few molecular diameters. Results from second-harmonic light scattering experiments presented here reveal long-range molecular orientation correlations in liquid water, where the molecular dipole orientation distribution has the form of a nearly pure transverse vector field. Spatial scales in the range 200-2000 nm are probed by the angle-dependent measurements and the observed correlations are thought to result from rotation-translation coupling in acoustic phonons in the liquid. [ABSTRACT FROM AUTHOR]

Water interfacing hydrated proteins carry properties distinct from those of the bulk and is often described as a separate entity, a "biological water." We address here the question of which dynamical and structural properties of hydration water deserve this distinction. The study focuses on different aspects of the density and orientational fluctuations of hydration water and the ability to separate them experimentally by combining depolarized light scattering with dielectric spectroscopy. We show that the dynamics of the density fluctuations of the hydration shells reflect the coupled dynamics of the solute and solvent and do not require a special distinction as "biological water." The orientations of shell water molecules carry dramatically different physics and do require a separation into a sub-ensemble. Depending on the property considered, the perturbation of water's orientational structure induced by the protein propagates 3-5 hydration shells into the bulk at normal temperature. [ABSTRACT FROM AUTHOR]

By simulating the rigid simple point charge extended model at temperature T = 300 K, the orientational relaxation of the OH-bond in water was investigated over short to intermediate timescales, within which molecules undergo inertial rotation and libration and then enter the rotational diffusion regime. According to the second-cumulant approximation, the orientational time correlation function (TCF) of each axis that is parallel or perpendicular to an OH-bond is related to an effective rotational density of states (DOS), which is determined using the power spectra of angular velocity autocorrelation functions (AVAFs) of the other two axes. In addition, the AVAF power spectrum of an axis was approximated as the rotational stable instantaneous normal mode (INM) spectrum of the axis. As described in a previous study [S. L. Chang, T. M. Wu, and C. Y. Mou, J. Chem. Phys. 121, 3605 (2004)], simulated molecules were classified into subensembles, according to either the local structures or the H-bond configurations of the molecules. For global molecules and the classified subensembles, the simulation results for the first- and second-rank orientational TCFs were compared with the second-cumulant predictions obtained using the effective rotational DOSs and the rotational stable- INM spectra. On short timescales, the OH-bond in water behaves similar to an inertial rotor and its anisotropy is lower than that of a water molecule. For molecules with three or more H-bonds, the OH-bond orientational TCFs are characterized by a recurrence, which is an indication for libration of the OH-bond. The recurrence can generally be described by the second-cumulant prediction obtained using the rotational stable-INM spectra; however, the orientational TCFs after the recurrence switch to a behavior similar to that predicted using the AVAF power spectra. By contrast, the OH-bond orientational TCFs of molecules initially connected with one or two H-bonds decay monotonically or exhibit a weak recurrence, indicating rapid relaxation into the rotational diffusion regime after the initial Gaussian decay. In addition to accurately describing the Gaussian decay, the second-cumulant predictions formulated using the rotational stable-INM spectra and the AVAF power spectra serve as the upper and lower limits, respectively, for the OH-bond orientational TCFs of these molecules after the Gaussian decay. [ABSTRACT FROM AUTHOR]

The technique of recoil ion momentum spectroscopy is employed to determine the complete momentum vectors for three fragment dissociation channels, [D2O](q+2) → (D+ + D+ + Oq+) with q = 1, 2, or 3 formed in collisions of isolated water molecules with 450 keV Xe9+ ions. The kinetic energy released in each of these dissociation channels is measured and angular correlations between the fragment momenta are determined. From the angular correlations of the three fragment ions with the direction of the incoming beam, a strong anisotropy in the emission of recoil fragments is reported. It is inferred that the molecular plane prefers to lie orthogonal to the incoming beam direction with certain orientations being more preferred than others and a clear signature of non-coplanar dissociation is also observed. [ABSTRACT FROM AUTHOR]

The recently developed evolutionary algorithm USPEX proved to be a tool that enables accurate and reliable prediction of structures. Here we extend this method to predict the crystal structure of polymers by constrained evolutionary search, where each monomeric unit is treated as a building block with fixed connectivity. This greatly reduces the search space and allows the initial structure generation with different sequences and packings of these blocks. The new constrained evolutionary algorithm is successfully tested and validated on a diverse range of experimentally known polymers, namely, polyethylene, polyacetylene, poly(glycolic acid), poly(vinyl chloride), poly(oxymethylene), poly(phenylene oxide), and poly (p-phenylene sulfide). By fixing the orientation of polymeric chains, this method can be further extended to predict the structures of complex linear polymers, such as all polymorphs of poly(vinylidene fluoride), nylon-6 and cellulose. The excellent agreement be-tween predicted crystal structures and experimentally known structures assures a major role of this approach in the efficient design of the future polymeric materials. [ABSTRACT FROM AUTHOR]

Measurements of the polarization dependence of hyper-Rayleigh scattering (HRS) by solutions of p-nitroaniline (PNA) in acetone-d6 were used to study molecular orientation correlations. The HRS observations were analyzed in terms of short range direct dipole-dipole correlations between the PNA molecules, a long range transverse polar mode for the PNA molecules, and a long range ion-induced longitudinal polar mode. The conclusion that long range correlations are present is opposite to that in previous work, due to previous neglect of the ion-induced contribution. Depolarized HRS not explained by local correlations appears above 0.1 M PNA concentration, and analysis of the HRS observations indicates strong orientation correlations with a range of 10 nm for the PNA molecules. [ABSTRACT FROM AUTHOR]

A carbon fiber-epoxy composite (CFEC) shock response in the through thickness orientation and in one of the fiber directions is significantly different. The hydrostatic pressure inside anisotropic materials depends on deviatoric strain components as well as volumetric strain. Non-linear effects, such as shock effects, can be incorporated through the volumetric straining in the material. Thus, a new basis is required to couple the anisotropic material stiffness and strength with anisotropic shock effects, associated energy dependence, and damage softening process. This article presents these constitutive equations for shock wave modeling of a damageable carbon fiber-epoxy composite. Modeling the effect of fiber orientation on the shock response of a CFEC has been performed using a generalized decomposition of the stress tensor [A. A. Lukyanov, Int. J. Plast. 24, 140 (2008)] and Mie-Grüneisen's extrapolation of high-pressure shock Hugoniot states to other thermodynamics states for shocked CFEC materials. The three-wave structure (non-linear anisotropic, fracture, and isotropic elastic waves) that accompanies damage softening process is also proposed in this work for describing CFEC behavior under shock loading which allows to remove any discontinuities observed in the linear case for relation between shock velocities and particle velocities [A. A. Lukyanov, Eur. Phys. J. B 74, 35 (2010)]. Different Hugoniot stress levels are obtained when the material is impacted in different directions; their good agreement with the experiment demonstrates that the anisotropic equation of state, strength, and damage model are adequate for the simulation of shock wave propagation within damageable CFEC material. Remarkably, in the through thickness orientation, the material behaves similar to a simple polymer whereas in the fiber direction, the proposed in this paper model explains an initial ramp, before at sufficiently high stresses, and a much faster rising shock above it. The numerical results for shock wave modeling using proposed constitutive equations are presented, discussed, and future studies are outlined. [ABSTRACT FROM AUTHOR]

A metal–interlayer–semiconductor (MIS) structure that is realized by inserting an ultrathin interlayer between a contact metal and a semiconductor has been investigated recently as a low-resistance non-alloyed contact structure. However, a comprehensive and systematical investigation of Schottky barrier height (SBH) modulation through the insertion of an interlayer depending on the contact surface orientation has not been conducted despite its importance for its use in multi-gate transistors. Therefore, in this work, the SBH modulation of the MIS contact structure for different contact surface orientations is systematically investigated, and a comprehensive analysis platform of the MIS contact structure is suggested. Two factors, (1) alleviation of Fermi-level pinning due to metal-induced gap states and interface states and (2) formation of the interface dipole, contribute to the SBH modulation in the MIS contact structure. Their contributions depending on the contact surface orientation are evaluated through a comparison of the contact structures on (100)- and (110)-oriented germanium (Ge). These factors and how they should be considered for a certain contact surface in Ge-channel multi-gate transistors are investigated. The investigation and the proposed analysis platform will contribute to the design of high-performance non-alloyed contact schemes for next-generation multi-gate transistors. [ABSTRACT FROM AUTHOR]

Measurements have been made near normal incidence of the two-dimensional spatial coherence of the acoustic field scattered from the lakebed in Seneca Lake, New York. In the test region, the lakebed consists of a series of sediment layers created by a sequence of distinct depositional processes. The spatial coherence length of the scattered field is shown to be dependent on the structure of the underlying sediment sequences. Significant ping-to-ping variability in the spatial coherence surface was also observed for each sediment sequence. This variability is quantified by a two-dimensional spatial coherence metric that measures the coherence lengths and asymmetric coherence surface orientation. The ping-to-ping variation of the surface asymmetry appears to be linked to the spatial isotropy of the sediment scattering strength. The scattering strength of the deepest observed sequence in the sub-bottom is the most spatially isotropic and the ping-to-ping variability of the coherence lengths and surface orientations are random. The scattering strength of the shallower sequences is spatially anisotropic and the coherence lengths and surface orientations show intervals of non-random ping-to-ping behavior. [ABSTRACT FROM AUTHOR]

We have successfully deposited Fe4N thin films with (111) out-of-plane orientation on thermally oxidized Si substrates using a facing-target-sputtering system. A Ta/Ru composite buffer layer was adopted to improve the (111) orientation of the Fe4N thin films. The N2 partial pressure and substrate temperature during sputtering were optimized to promote the formation of the Fe4N phase. Furthermore, we measured the transport spin polarization of (111) oriented Fe4N by the point contact Andreev reflection (PCAR) technique. The spin polarization ratio was determined to be 0.50 using a modified BTK model. The film thickness dependence of the spin polarization was also investigated. The spin polarization of Fe4N measured by PCAR does not show degradation as the sample thickness was reduced to 10nm. [ABSTRACT FROM AUTHOR]

The selective epitaxial growth of Si1-xGex and the related strain properties were studied. Epitaxial Si1-xGex films were deposited on (100) and (110) orientation wafers and on patterned Si wafers with recessed source and drain structures via ultrahigh vacuum chemical vapor deposition using different growing steps and Ge concentrations. The stepwise process was split into more than 6 growing steps that ranged in thicknesses from a few to 120 nm in order to cover the wide stages of epitaxial growth. The growth rates of SiGe on the plane and patterned wafers were examined and a dependence on the surface orientation was identified. As the germanium concentration increased, defects were generated with thinner Si1-xGex growth. The defect generation was the result of the strain evolution which was examined for channel regions with a Si1-xGex source/drain (S/D) structure. [ABSTRACT FROM AUTHOR]

We investigated the dependence of absolute SnS band-edge energies on surface orientation using density functional theory and GW method for all surfaces with Miller indices -3 ≤ h; k; l ≤ 3 and found variations as large as 0.9 eV as a function of (hkl). Variations of this magnitude may affect significantly the performance of photovoltaic devices based on polycrystalline SnS thin-films and, in particular, may contribute to the relatively low measured open circuit voltage of SnS solar cells. X-ray diffraction measurements confirm that our thermally evaporated SnS films exhibit a wide distribution of different grain orientations, and the results of Kelvin force microscopy support the theoretically predicted variations of the absolute band-edge energies. [ABSTRACT FROM AUTHOR]

Orientation-engineered 0.755(Bi0.5Na0.5)TiO3-0.065BaTiO3-0.18SrTiO3 thin films deposited on Nb doped SrTiO3 (N:STO) single crystalline (001), (110), and (111) substrates via a sol-gel process were investigated. Highly epitaxial growth was observed in the as-deposited thin films. Excellent piezoelectric properties are exhibited by the (111) oriented thin films with the highest strain level (0.32%) and local effective piezoelectric coefficient (d33=210 pm/V). Strong orientation dependence of piezoelectric properties on the thin films is attributed to the relative alignment of crystallites and spontaneous polarization vector. These findings are of great significance for piezo-micro electro mechanical systems. [ABSTRACT FROM AUTHOR]

Two high-k dielectric materials (Al2O3 and HfO2) were deposited on n-type (100) and (110) InAs surface orientations to investigate physical properties of the oxide/ semiconductor interfaces and the interface trap density (Dit). X-ray photoelectron spectroscopy analyses (XPS) for native oxides of (100) and (110) as-grown n-InAs epi wafers show an increase in As-oxide on the (100) surface and an increase in InOx on the (110) surface. In addition, XPS analyses of high-k (Al2O3 and HfO2) on n-InAs epi show that the intrinsic native oxide difference between (100) and (110) epi surfaces were eliminated by applying conventional in-situ pre-treatment (TriMethyAluminium (TMA)) before the high-k deposition. The capacitance-voltage (C-V) characterization of HfO2 and Al2O3 MOSCAPs on both types of n-InAs surfaces shows very similar C-V curves. The interface trap density (Dit) profiles show Dit minima of 6.1 × 1012/6.5 × 1012 and 6.6 × 1012/7.3 × 1012 cm-2 eV-1 for Al2O3 and HfO2, respectively for (100) and (110) InAs surfaces. The similar interface trap density (Dit) on (100) and (110) surface orientation were observed, which is beneficial to future InAs FinFET device with both (100) and (110) surface channel orientations present. [ABSTRACT FROM AUTHOR]

We determine the orientation-resolved interfacial free energy between a body-centered-cubic (bcc) crystal and the coexisting fluid for a many-particle system interacting via a Yukawa pair potential. For two different screening strengths, we compare results from molecular dynamics computer simulations, density functional theory, and a phase-field-crystal approach. Simulations predict an almost orientationally isotropic interfacial free energy of 0.12kBT/a2 (with kBT denoting the thermal energy and a the mean interparticle spacing), which is independent of the screening strength. This value is in reasonable agreement with our Ramakrishnan-Yussouff density functional calculations, while a high-order fitted phase-field-crystal approach gives about 2-3 times higher interfacial free energies for the Yukawa system. Both field theory approaches also give a considerable anisotropy of the interfacial free energy. Our result implies that, in the Yukawa system, bcc crystal-fluid free energies are a factor of about 3 smaller than face-centered-cubic crystal-fluid free energies. [ABSTRACT FROM AUTHOR]

To understand the influence of reactant internal excitation and orientation on the dissociative chemisorption of water on Cu(111), a quasi-seven-dimensional quantum dynamics study has been carried out on a refined potential energy surface (PES). The new PES was modified in the asymptotic region to allow an accurate characterization of the H2O ro-vibrational levels. The mode selectivity of the reaction was reexamined on the new PES and found to be consistent with our earlier work. To rationalize the observed mode selectivity, a vibrationally adiabatic reaction path model was determined on this PES. Furthermore, the reactivity for various rotationally excited H2O was investigated. It is shown that even low rotational excitation in H2O can either enhance or inhibit the reaction and the reactivity depends on the orientation of the impinging molecule. [ABSTRACT FROM AUTHOR]

We engineered various orientations of NiO layers for NiO-based heterostructures (NiO/Au/STO) to investigate their effects on the generation of hot electrons and holes. Our calculation and experimental results suggested that bandgap engineering and the orientation of the hole transport layer (NiO) were crucial elements for the optimization of photoelectric responses. The (100)-orientated NiO/Au/STO achieved the highest photo-current density (∼30 μA/cm2) compared with (111) and (110)-orientated NiO films, which was attributed to the (100) films's lowest effective mass of photogenerated holes (∼1.82 m0) and the highest efficiency of separating and transferring electron-holes of the (100)-orientated sample. Our results opened a direction to design a high efficiency photoelectric solar cell. [ABSTRACT FROM AUTHOR]

Valence band structure and surface states of InN with (0001), (000-1), (1-100), and (11-20) orientation were investigated in situ after growth using photoelectron spectroscopy. Depending on surface orientation, different occupied surface states are identified and differentiated from bulk contributions. For N-polar, m-plane, and a-plane InN, the surface states are located at the valence band maximum, while In-polar InN features surface states close to the Fermi level. The surface band alignment correlates with the position of surface states. For InN(0001), a much larger surface downward band bending is observed compared to N-polar, m-plane, and a-plane InN, where almost flat band conditions occur. [ABSTRACT FROM AUTHOR]

AlSb is grown by molecular beam epitaxy. The evolution and the relaxation of the deposited AlSb layer is investigated by synchrotron-based in situ grazing incidence x-ray diffraction (GID), and the analysis of the real space distribution is performed by atomic force microscopy. AlSb forms islands with (111)A polarity and {110} surface orientations with different side facets following the Volmer-Weber growth mode. GID investigations reveal facet rods originating from AlSb{110} islands. It is shown that a concentration of only 0.7% AlSb{110} oriented domains influences the diffraction pattern in such a way that additional crystal truncation rods parallel to the surface appear. [ABSTRACT FROM AUTHOR]