Showing papers on "Charge density published in 2014"

Order of Magnitude Smaller Limit on the Electric Dipole Moment of the Electron

Abstract: The Standard Model of particle physics is known to be incomplete. Extensions to the Standard Model, such as weak-scale supersymmetry, posit the existence of new particles and interactions that are asymmetric under time reversal (T) and nearly always predict a small yet potentially measurable electron electric dipole moment (EDM), d(e), in the range of 10(-27) to 10(-30) e·cm. The EDM is an asymmetric charge distribution along the electron spin (S(→)) that is also asymmetric under T. Using the polar molecule thorium monoxide, we measured d(e) = (-2.1 ± 3.7stat ± 2.5syst) × 10(-29) e·cm. This corresponds to an upper limit of |d(e)| < 8.7 × 10(-29) e·cm with 90% confidence, an order of magnitude improvement in sensitivity relative to the previous best limit. Our result constrains T-violating physics at the TeV energy scale.

A photoinduced metal-like phase of monoclinic VO2 revealed by ultrafast electron diffraction

Abstract: The complex interplay among several active degrees of freedom (charge, lattice, orbital, and spin) is thought to determine the electronic properties of many oxides. We report on combined ultrafast electron diffraction and infrared transmissivity experiments in which we directly monitored and separated the lattice and charge density reorganizations that are associated with the optically induced semiconductor-metal transition in vanadium dioxide (VO2). By photoexciting the monoclinic semiconducting phase, we were able to induce a transition to a metastable state that retained the periodic lattice distortion characteristic of the semiconductor but also acquired metal-like mid-infrared optical properties. Our results demonstrate that ultrafast electron diffraction is capable of following details of both lattice and electronic structural dynamics on the ultrafast time scale.

Maximum surface charge density for triboelectric nanogenerators achieved by ionized-air injection: methodology and theoretical understanding.

Abstract: For the maximization of the surface charge density in triboelectric nanogenerators, a new method of injecting single-polarity ions onto surfaces is introduced for the generation of surface charges. The triboelectric nanogenerator's output power gets greatly enhanced and its maximum surface charge density is systematically studied, which shows a huge room for the improvement of the output of triboelectric nanogenerators by surface modification.

Novel metals and insulators from holography

Abstract: Using simple holographic models in D = 4 spacetime dimensions we construct black hole solutions dual to d = 3 CFTs at finite charge density with a Q-lattice deformation. At zero temperature we find new ground state solutions, associated with broken translation invariance in either one or both spatial directions, which exhibit insulating or metallic behaviour depending on the parameters of the holographic theory. For low temperatures and small frequencies, the real part of the optical conductivity exhibits a power-law behaviour. We also obtain an expression for the the DC conductivity at finite temperature in terms of horizon data of the black hole solutions.

Size Dependent Surface Charge Properties of Silica Nanoparticles

Abstract: Nanoparticle surface charge density plays an important role in many applications, such as drug delivery and cellular uptake. In this study, surface charge properties of silica nanoparticles with different sizes are studied using a multi-ion surface charge-regulation model. In contrast to most previous studies utilizing constant surface charge, protonation and deprotonation surface reactions are used to obtain the local surface charge, which depends on the particle size and electrolyte solution properties, including the salt concentration and pH. For a fixed particle size, the magnitude of the surface charge typically increases with an increase in pH or background salt concentration. For fixed background salt concentration and pH, the magnitude of surface charge decreases with an increase in the particle size and reaches a constant when the particle size exceeds a critical value. Size dependent surface charge is further characterized by the ratio of electrical double layer thickness to the particle diamete...

Electronic couplings for molecular charge transfer: benchmarking CDFT, FODFT, and FODFTB against high-level ab initio calculations.

Abstract: We introduce a database (HAB11) of electronic coupling matrix elements (Hab) for electron transfer in 11 π-conjugated organic homo-dimer cations. High-level ab inito calculations at the multireference configuration interaction MRCI+Q level of theory, n-electron valence state perturbation theory NEVPT2, and (spin-component scaled) approximate coupled cluster model (SCS)-CC2 are reported for this database to assess the performance of three DFT methods of decreasing computational cost, including constrained density functional theory (CDFT), fragment-orbital DFT (FODFT), and self-consistent charge density functional tight-binding (FODFTB). We find that the CDFT approach in combination with a modified PBE functional containing 50% Hartree-Fock exchange gives best results for absolute Hab values (mean relative unsigned error = 5.3%) and exponential distance decay constants β (4.3%). CDFT in combination with pure PBE overestimates couplings by 38.7% due to a too diffuse excess charge distribution, whereas the ec...

The electric double layer has a life of its own

Abstract: Using molecular dynamics simulations with recently developed importance sampling methods, we show that the differential capacitance of a model ionic liquid based double-layer capacitor exhibits an anomalous dependence on the applied electrical potential. Such behavior is qualitatively incompatible with standard mean-field theories of the electrical double layer, but is consistent with observations made in experiment. The anomalous response results from structural changes induced in the interfacial region of the ionic liquid as it develops a charge density to screen the charge induced on the electrode surface. These structural changes are strongly influenced by the out-of-plane layering of the electrolyte and are multifaceted, including an abrupt local ordering of the ions adsorbed in the plane of the electrode surface, reorientation of molecular ions, and the spontaneous exchange of ions between different layers of the electrolyte close to the electrode surface. The local ordering exhibits signatures of a first-order phase transition, which would indicate a singular charge-density transition in a macroscopic limit.

Non-thermal separation of electronic and structural orders in a persisting charge density wave

Abstract: The electronic and structural components of charge density waves occurring in layered transition metal dichalcogenides are known to be interdependent, yet have only been probed in separate measurements. Now, a broadband terahertz spectroscopy approach that monitors the evolution of these two order parameters simultaneously is demonstrated.

Visualization of charge propagation along individual pili proteins using ambient electrostatic force microscopy

Abstract: The nanoscale imaging of charge flow in proteins is crucial to understanding several life processes, including respiration, metabolism and photosynthesis. However, existing imaging methods are only effective under non-physiological conditions or are limited to photosynthetic proteins. Here, we show that electrostatic force microscopy can be used to directly visualize charge propagation along pili of Geobacter sulfurreducens with nanometre resolution and under ambient conditions. Charges injected at a single point into individual, untreated pili, which are still attached to cells, propagated over the entire filament. The mobile charge density in the pili, as well as the temperature and pH dependence of the charge density, were similar to those of carbon nanotubes and other organic conductors. These findings, coupled with a lack of charge propagation in mutated pili that were missing key aromatic amino acids, suggest that the pili of G. sulfurreducens function as molecular wires with transport via delocalized charges, rather than the hopping mechanism that is typical of biological electron transport.

Quantifying Artifacts in Ewald Simulations of Inhomogeneous Systems with a Net Charge

Abstract: Ewald summation, which has become the de facto standard for computing electrostatic interactions in biomolecular simulations, formally requires that the simulation box is neutral. For non-neutral systems, the Ewald algorithm implicitly introduces a uniform background charge distribution that effectively neutralizes the simulation box. Because a uniform distribution of counter charges typically deviates from the spatial distribution of counterions in real systems, artifacts may arise, in particular in systems with an inhomogeneous dielectric constant. Here, we derive an analytical expression for the effect of using an implicit background charge instead of explicit counterions, on the chemical potential of ions in heterogeneous systems, which (i) provides a quantitative criterium for deciding if the background charge offers an acceptable trade-off between artifacts arising from sampling problems and artifacts arising from the homogeneous background charge distribution, and (ii) can be used to correct this artifact in certain cases. Our model quantifies the artifact in terms of the difference in charge density between the non-neutral system with a uniform neutralizing background charge and the real neutral system with a physically correct distribution of explicit counterions. We show that for inhomogeneous systems, such as proteins and membranes in water, the artifact manifests itself by an overstabilization of ions inside the lower dielectric by tens to even hundreds kilojoules per mole. We have tested the accuracy of our model in molecular dynamics simulations and found that the error in the calculated free energy for moving a test charge from water into hexadecane, at different net charges of the system and different simulation box sizes, is correctly predicted by the model. The calculations further confirm that the incorrect distribution of counter charges in the simulation box is solely responsible for the errors in the PMFs.

The electric double layer has a life of its own

Abstract: Using molecular dynamics simulations with recently developed importance sampling methods, we show that the differential capacitance of a model ionic liquid based double-layer capacitor exhibits an anomalous dependence on the applied electrical potential. Such behavior is qualitatively incompatible with standard mean-field theories of the electrical double layer, but is consistent with observations made in experiment. The anomalous response results from structural changes induced in the interfacial region of the ionic liquid as it develops a charge density to screen the charge induced on the electrode surface. These structural changes are strongly influenced by the out-of-plane layering of the electrolyte and are multifaceted, including an abrupt local ordering of the ions adsorbed in the plane of the electrode surface, reorientation of molecular ions, and the spontaneous exchange of ions between different layers of the electrolyte close to the electrode surface. The local ordering exhibits signatures of a first-order phase transition, which would indicate a singular charge-density transition in a macroscopic limit.

Global performance of covariant energy density functionals: ground state observables of even-even nuclei and the estimate of theoretical uncertainties

Abstract: Covariant density functional theory is a modern theoretical tool for the description of nuclear structure phenomena. The current investigation aims at the global assessment of the accuracy of the description of the ground state properties of even-even nuclei. We also estimate theoretical uncertainties defined here as the spreads of predictions within four covariant energy density functionals in known regions of the nuclear chart and their propagation towards the neutron drip line. Large-scale axial relativistic Hartree-Bogoliubov calculations are performed for all $Z\ensuremath{\le}104$ even-even nuclei between the two-proton and two-neutron drip lines with four modern covariant energy density functionals such as NL3*, DD-ME2, DD-ME$\ensuremath{\delta}$, and DD-PC1. The physical observables of interest include the binding energies, two-particle separation energies, charge quadrupole deformations, isovector deformations, charge radii, neutron skin thicknesses, and the positions of the two-proton and two-neutron drip lines. The predictions for the two-neutron drip line are also compared in a systematic way with the ones obtained in nonrelativistic models.

Novel metals and insulators from holography

Abstract: Using simple holographic models in $D=4$ spacetime dimensions we construct black hole solutions dual to $d=3$ CFTs at finite charge density with a Q-lattice deformation. At zero temperature we find new ground state solutions with broken translation invariance, either in one or both spatial directions, which exhibit insulating or metallic behaviour depending on the parameters of the holographic theory. For low temperatures and small frequencies, the real part of the optical conductivity has a power-law behaviour, with the exponent determined by the ground state. We also obtain an expression for the the DC conductivity at finite temperature in terms of horizon data of the black hole solutions.

Structure of water at charged interfaces: a molecular dynamics study.

Abstract: The properties of water molecules located close to an interface deviate significantly from those observed in the homogeneous bulk liquid. The length scale over which this structural perturbation persists (the so-called interfacial depth) is the object of extensive investigations. The situation is particularly complicated in the presence of surface charges that can induce long-range orientational ordering of water molecules, which in turn dictate diverse processes, such as mineral dissolution, heterogeneous catalysis, and membrane chemistry. To characterize the fundamental properties of interfacial water, we performed molecular dynamics (MD) simulations on alkali chloride solutions in the presence of two types of idealized charged surfaces: one with the charge density localized at discrete sites and the other with a homogeneously distributed charge density. We find that, in addition to a diffuse region where water orientation shows no layering, the interface region consists of a "compact layer" of solvent next to the surface that is not described in classical electric double layer theories. The depth of the diffuse solvent layer is sensitive to the type of charge distributions on the surface and the ionic strength. Simulations of the aqueous interface of a realistic model of negatively charged amorphous silica show that the water orientation and the distribution of ions strongly depend on the identity of the cations (Na(+) vs Cs(+)) and are not well represented by a simplistic homogeneous charge distribution model. While the compact layer shows different solvent net orientation and depth for Na(+) vs Cs(+), the depth (~1 nm) of the diffuse layer of oriented waters is independent of the identity of the cation screening the charge. The details of interfacial water orientation revealed here go beyond the traditionally used double and triple layer models and provide a microscopic picture of the aqueous/mineral interface that complements recent surface specific experimental studies.

Metal-Insulator Transition by Holographic Charge Density Waves

Abstract: We construct a gravity dual for charge density waves (CDWs) in which the translational symmetry along one spatial direction is spontaneously broken. Our linear perturbation calculation on the gravity side produces the frequency dependence of the optical conductivity, which exhibits the two familiar features of CDWs, namely, the pinned collective mode and gapped single-particle excitation. These two features indicate that our gravity dual also provides a new mechanism to implement the metal to insulator phase transition by CDWs, which is further confirmed by the fact that dc conductivity decreases with the decreased temperature below the critical temperature.

Single-Particle Spectroscopy Reveals Heterogeneity in Electrochemical Tuning of the Localized Surface Plasmon

Abstract: A hyperspectral imaging method was developed that allowed the identification of heterogeneous plasmon response from 50 nm diameter gold colloidal particles on a conducting substrate in a transparent three-electrode spectroelectrochemical cell under non-Faradaic conditions. At cathodic potentials, we identified three distinct behaviors from different nanoparticles within the same sample: irreversible chemical reactions, reversible chemical reactions, and reversible charge density tuning. The irreversible reactions in particular would be difficult to discern in alternate methodologies. Additional heterogeneity was observed when single nanoparticles demonstrating reversible charge density tuning in the cathodic regime were measured dynamically in anodic potential ranges. Some nanoparticles that showed charge density tuning in the cathodic range also showed signs of an additional chemical tuning mechanism in the anodic range. The expected changes in nanoparticle free-electron density were modeled using a char...

A conclusive view on charge generation, recombination, and extraction in As-prepared and annealed P3HT:PCBM blends: combined experimental and simulation work

Abstract: Time-delayed collection field (TDCF) and bias-amplified charge extraction (BACE) are applied to as-prepared and annealed poly(3-hexylthiophene):[6,6]-phenyl C-71 butyric acid methyl ester (P3HT:PCBM) blends coated from chloroform. Despite large differences in fill factor, short-circuit current, and power conversion efficiency, both blends exhibit a negligible dependence of photogeneration on the electric field and strictly bimolecular recombination (BMR) with a weak dependence of the BMR coefficient on charge density. Drift-diffusion simulations are performed using the measured coefficients and mobilities, taking into account bimolecular recombination and the possible effects of surface recombination. The excellent agreement between the simulation and the experimental data for an intensity range covering two orders of magnitude indicates that a field-independent generation rate and a density-independent recombination coefficient describe the current-voltage characteristics of the annealed P3HT: PCBM devices, while the performance of the as-prepared blend is shown to be limited by space charge effects due to a low hole mobility. Finally, even though the bimolecular recombination coefficient is small, surface recombination is found to be a negligible loss mechanism in these solar cells.

A scaled-ionic-charge simulation model that reproduces enhanced and suppressed water diffusion in aqueous salt solutions

Abstract: Non-polarizable models for ions and water quantitatively and qualitatively misrepresent the salt concentration dependence of water diffusion in electrolyte solutions. In particular, experiment shows that the water diffusion coefficient increases in the presence of salts of low charge density (e.g., CsI), whereas the results of simulations with non-polarizable models show a decrease of the water diffusion coefficient in all alkali halide solutions. We present a simple charge-scaling method based on the ratio of the solvent dielectric constants from simulation and experiment. Using an ion model that was developed independently of a solvent, i.e., in the crystalline solid, this method improves the water diffusion trends across a range of water models. When used with a good-quality water model, e.g., TIP4P/2005 or E3B, this method recovers the qualitative behaviour of the water diffusion trends. The model and method used were also shown to give good results for other structural and dynamic properties including solution density, radial distribution functions, and ion diffusion coefficients.

Thickness dependence of the charge-density-wave transition temperature in VSe2

Abstract: A set of three-dimensional charge-density-wave (3D CDW) VSe2 nano-flakes with different thicknesses were obtained by the scotch tape-based micro-mechanical exfoliation method. Resistivity measurements showed that the 3D CDW transition temperature Tp decreases systematically from 105 K in bulk to 81.8 K in the 11.6 nm thick flake. The Hall resistivity ρxy of all the flakes showed a linear dependent behavior against the magnetic field with a residual electron concentration of the order of ∼1021 cm−3 at 5 K. The electron concentration n increases slightly as the thickness d decreases, possibly due to the CDW gap is reduced with the decrease of the thickness.

Experimental Charge Density Study of a Silylone

Abstract: An experimental and theoretical charge density study confirms the interpretation of (cAAC)2Si as a silylone to be valid. Two separated VSCCs present in the non-bonding region of the central silicon are indicative for two lone pairs. In the experiment, both the two crystallographically independent Si-C bond lengths and ellipticities vary notably. It is only the cyclohexyl derivative that shows significant differences in these values, both in the silylones and the germylones. Only by calculating increasing spheres of surrounding point charges we were able to recover the changes in the properties of the charge density distribution caused by weak intermolecular interactions. The nitrogen-carbene-carbon bond seems to have a significant double-bond character, indicating a singlet state for the carbene carbon, which is needed for donor acceptor bonding. Thus the sum of bond angles at the nitrogen atoms seems to be a reasonable estimate for singlet versus triplet state of cAACs.

Band structure engineering of monolayer MoS2 on h-BN: first-principles calculations

Abstract: We have carried out first-principles calculations and theoretical analysis to explore the structural and electronic properties of MoS2/n-h-BN heterostructures consisting of monolayer MoS2 on top of h-BN substrates with one to five layers. We find that the MoS2/n-h-BN heterostructures show indirect bandgap features with both of CBM (in the K point) and VBM (in the ? point) localized on the monolayer MoS2. Difference charge density and surface bands indicate there is no obvious charge exchange in the heterostructure systems. We show that the changes from a direct bandgap in monolayer free-stranding MoS2 to an indirect bandgap in MoS2/n-h-BN heterostructure is induced by the strain. Moreover, we find that the bandgaps of MoS2/n-h-BN heterostructures decrease with increasing number of h-BN layers, which is proposed to result from the different strain distributions in MoS2 due to the varieties of lattice mismatch rates between MoS2 and h-BN layers. Our results suggest that the MoS2/n-h-BN heterostructure could serve as a prototypical example for band structure engineering of 2D crystals with atomic layer precision.

An optimized interatomic potential for Cu?Ni alloys with the embedded-atom method

Abstract: We have developed a semi-empirical and many-body type model potential using a modified charge density profile for Cu–Ni alloys based on the embedded-atom method (EAM) formalism with an improved optimization technique. The potential is determined by fitting to experimental and first-principles data for Cu, Ni and Cu–Ni binary compounds, such as lattice constants, cohesive energies, bulk modulus, elastic constants, diatomic bond lengths and bond energies. The generated potentials were tested by computing a variety of properties of pure elements and the alloy of Cu, Ni: the melting points, alloy mixing enthalpy, lattice specific heat, equilibrium lattice structures, vacancy formation and interstitial formation energies, and various diffusion barriers on the (100) and (111) surfaces of Cu and Ni.

Quantifying Charge Extraction in Organic Solar Cells: The Case of Fluorinated PCPDTBT.

Abstract: We introduce a new and simple method to quantify the effective extraction mobility in organic solar cells at low electric fields and charge carrier densities comparable to operation conditions under one sun illumination. By comparing steady-state carrier densities at constant illumination intensity and under open-circuit conditions, the gradient of the quasi-Fermi potential driving the current is estimated as a function of external bias and charge density. These properties are then related to the respective steady-state current to determine the effective extraction mobility. The new technique is applied to different derivatives of the well-known low-band-gap polymer PCPDTBT blended with PC70BM. We show that the slower average extraction due to lower mobility accounts for the moderate fill factor when solar cells are fabricated with mono- or difluorinated PCPDTBT. This lower extraction competes with improved generation and reduced nongeminate recombination, rendering the monofluorinated derivative the most efficient donor polymer.

Controllably Interfacing with Metal: A Strategy for Enhancing CO Oxidation on Oxide Catalysts by Surface Polarization

Abstract: Heterogeneous catalysis often involves charge transfer from catalyst surface to adsorbed molecules, whose activity thus depends on the surface charge density of catalysts. Here, we demonstrate a unique solution-phase approach to achieve controllable interfacial lengths in oxide-metal hybrid structures. Resulting from their different work functions, surface polarization is induced by the Ag-CuO interface and acts to tailor the surface charge state of CuO. As a result, the designed hybrid catalysts exhibit enhanced intrinsic activities in catalyzing CO oxidation in terms of apparent activation energy, as compared with their counterparts. Moreover, the CO conversion rate can be enhanced by maximizing the Ag-CuO interfacial length and thus the number of active sites on the CuO. This work provides a new strategy for tuning catalytic performance by controlling interface in hybrid catalysts.

Interface Charge Engineering for Enhancement-Mode GaN MISHEMTs

Abstract: We demonstrate an efficient approach to engineer the dielectric/AlGaN positive interface fixed charges by oxygen plasma and post-metallization anneal. Significant suppression of interface fixed charges from 2 × 1013 to 8 × 1012 cm-2 was observed. Experimental and theoretical electron mobility characteristics and the impact of remote impurity scattering were investigated. The reduction in oxide/semiconductor interface charge density leads to an increase of electron mobility, and enables a positive threshold voltage.

Air stable n-doping of WSe2 by silicon nitride thin films with tunable fixed charge density

Abstract: Stable n-doping of WSe2 using thin films of SiNx deposited on the surface via plasma-enhanced chemical vapor deposition is presented. Positive fixed charge centers inside SiNx act to dope WSe2 thin flakes n-type via field-induced effect. The electron concentration in WSe2 can be well controlled up to the degenerate limit by simply adjusting the stoichiometry of the SiNx through deposition process parameters. For the high doping limit, the Schottky barrier width at the metal/WSe2 junction is significantly thinned, allowing for efficient electron injection via tunneling. Using this doping scheme, we demonstrate air-stable WSe2 n-MOSFETs with a mobility of ∼70 cm2/V s.

Visualizing the interfacial evolution from charge compensation to metallic screening across the manganite metal-insulator transition

Abstract: The nature of interfacial reconstructions at polar interfaces between transition metal oxides is known to be complex and difficult to characterize. Here, the authors quantify the atomic-scale charge distribution for manganite–titanate interfaces, spanning the manganite metal–insulator transition.