Charge Polarization Effects Research Articles

Advances in Charge Displacement Analysis.

We define new general density-based descriptors for the quantification of charge transfer and polarization effects associated with the interaction between two fragments and the formation of a chemical bond. Our aim is to provide a simple yet accurate picture of a chemical interaction by condensing the information on the charge rearrangement accompanying it into a few chemically meaningful parameters. These charge displacement (CD) parameters quantify the total charge displaced upon bond formation and decompose it into a charge transfer component between the fragments and charge rearrangements taking place within the fragments. We then show how the new parameters can be easily calculated using the well-known CD function, which describes the charge flow along a chosen axis accompanying the formation of a bond. The approach presented here can be useful in a wide variety of contexts, ranging from weak interactions to electronic excitations to coordination chemistry. In particular, we discuss here how the scheme can be used for the characterization of the donation and back-donation components of metal-ligand bonds, in combination with the natural orbitals for chemical valence (NOCV) theory. In doing so, we discuss the interesting relationship between the proposed parameters and the corresponding NOCV eigenvalues, commonly used as a measure of the electron charge displacement associated with a given bonding contribution. As a prototype case study, we investigate the bond between a N-heterocyclic carbene and different metallic fragments. Finally, we show that our approach can be used in combination with the energy decomposition of the extended transition state method, providing an estimate of both charge transfer and polarization contributions to the interaction energy.

Unusual dimensionality effects and surface charge density in 2D Mg(OH)2.

We present two-dimensional Mg(OH)2 sheets and their vertical heterojunctions with CVD-MoS2 for the first time as flexible 2D insulators with anomalous lattice vibration and chemical and physical properties. New hydrothermal crystal growth technique enabled isolation of environmentally stable monolayer Mg(OH)2 sheets. Raman spectroscopy and vibrational calculations reveal that the lattice vibrations of Mg(OH)2 have fundamentally different signature peaks and dimensionality effects compared to other 2D material systems known to date. Sub-wavelength electron energy-loss spectroscopy measurements and theoretical calculations show that Mg(OH)2 is a 6 eV direct-gap insulator in 2D, and its optical band gap displays strong band renormalization effects from monolayer to bulk, marking the first experimental confirmation of confinement effects in 2D insulators. Interestingly, 2D-Mg(OH)2 sheets possess rather strong surface polarization (charge) effects which is in contrast to electrically neutral h-BN materials. Using 2D-Mg(OH)2 sheets together with CVD-MoS2 in the vertical stacking shows that a strong change transfer occurs from n-doped CVD-MoS2 sheets to Mg(OH)2, naturally depleting the semiconductor, pushing towards intrinsic doping limit and enhancing overall optical performance of 2D semiconductors. Results not only establish unusual confinement effects in 2D-Mg(OH)2, but also offer novel 2D-insulating material with unique physical, vibrational, and chemical properties for potential applications in flexible optoelectronics.

A physics-based potential and electric field model of a nanoscale rectangular high-K gate dielectric HEMT

In this paper, we have developed a physics-based model for surface potential, channel potential, electric field and drain current for AlGaN/GaN high electron mobility transistor with high-K gate dielectric using two-dimensional Poisson equation under full depletion approximation with the inclusion of effect of polarization charges. The accuracy of the model has been verified and is found to be in good agreement with the simulated results.

Quantum effects in cation interactions with first and second coordination shell ligands in metalloproteins.

Despite decades of investigations, the principal mechanisms responsible for the high affinity and specificity of proteins for key physiological cations K+, Na+, and Ca2+ remain a hotly debated topic. At the core of the debate is an apparent need (or lack thereof) for an accurate description of the electrostatic response of the charge distribution in a protein to the binding of an ion. These effects range from partial electronic polarization of the directly ligating atoms to long-range effects related to partial charge transfer and electronic delocalization effects. While accurate modeling of cation recognition by metalloproteins warrants the use of quantum-mechanics (QM) calculations, the most popular approximations used in major biomolecular simulation packages rely on the implicit modeling of electronic polarization effects. That is, high-level QM computations for ion binding to proteins are desirable, but they are often unfeasible, because of the large size of the reactive-site models and the need to sample conformational space exhaustively at finite temperature. Several solutions to this challenge have been proposed in the field, ranging from the recently developed Drude polarizable force-field for simulations of metalloproteins to approximate tight-binding density functional theory (DFTB). To delineate the usefulness of different approximations, we examined the accuracy of three recent and commonly used theoretical models and numerical algorithms, namely, CHARMM C36, the latest developed Drude polarizable force fields, and DFTB3 with the latest 3OB parameters. We performed MD simulations for 30 cation-selective proteins with high-resolution X-ray structures to create ensembles of structures for analysis with different levels of theory, e.g., additive and polarizable force fields, DFTB3, and DFT. The results from DFT computations were used to benchmark CHARMM C36, Drude, and DFTB3 performance. The explicit modeling of quantum effects unveils the key electrostatic properties of the protein sites and the importance of specific ion-protein interactions. One of the most interesting findings is that secondary coordination shells of proteins are noticeably perturbed in a cation-dependent manner, showing significant delocalization and long-range effects of charge transfer and polarization upon binding Ca2+.

Profiling of Current Transients in Capacitor Type Diamond Sensors

The operational characteristics of capacitor-type detectors based on HPHT and CVD diamond have been investigated using perpendicular and parallel injection of carrier domain regimes. Simulations of the drift-diffusion current transients have been implemented by using dynamic models based on Shockley-Ramo’s theorem, under injection of localized surface domains and of bulk charge carriers. The bipolar drift-diffusion regimes have been analyzed for the photo-induced bulk domain (packet) of excess carriers. The surface charge formation and polarization effects dependent on detector biasing voltage have been revealed. The screening effects ascribed to surface charge and to dynamics of extraction of the injected bulk excess carrier domain have been separated and explained. The parameters of drift mobility of the electrons μe = 4000 cm2/Vs and holes μh = 3800 cm2/Vs have been evaluated for CVD diamond using the perpendicular profiling of currents. The coefficient of carrier ambipolar diffusion Da = 97 cm2/s and the carrier recombination lifetime τR,CVD ≌ 110 ns in CVD diamond were extracted by combining analysis of the transients of the sensor current and the microwave probed photoconductivity. The carrier trapping with inherent lifetime τR,HPHT ≌ 2 ns prevails in HPHT diamond.

Effect of Spontaneous Polarization Charges on the Electron Mobility in ZnO Surface Quantum Wells

We present a theoretical study of the effect due to spontaneous polarization of ZnO on the low-temperature mobility of the two-dimensional electron gas (2DEG) in a ZnO surface quantum well (SFQW). We proved that for the O-polar face this causes an attraction of electrons by the positive charges bound on the surface, while for the Zn-polar face a repulsion of them far away therefrom by the negative bound charges of the same magnitude. Accordingly, surface roughness scattering is drastically enhanced in the former case, but reduced in the latter one. Therefore, the low-% temperature 2DEG mobility in ZnO SFQWs with O-polar face is found to be dominated by surface roughness. Our theory was illustrated for the sample prepared by bombardment of the O-polar face by 100-eV hydrogen ions. The surface roughness scattering enables an explanation of the 2DEG mobility, especially, the reason of low values for the mobility in the dependence from the carrier density which has not been understood when starting from impurity scattering.

Space charge polarization-induced symmetrical negative resistive switching in individual p-type GeSe2:Bi superstructure nanobelts for non-volatile memory

Two-terminal devices based on p-type GeSe2:Bi nanobelts show excellent symmetrical nonvolatile negative resistive switching memory behavior, originating from trap-induced space charge polarization effect.

Explicit Drug Re-positioning: Predicting Novel Drug-Target Interactions of the Shelved Molecules with QM/MM Based Approaches.

With the demand to enhance the speed of the drug discovery process there has been an increased usage of computational approaches in drug discovery studies. However because of their probabilistic outcomes, the challenge is to exactly mimic the natural environment which can provide the exact charge polarization effect while estimating the binding energy between protein and ligand. There has been a large number of scoring functions from simple one to the complex one available for estimating binding energy. The quantum mechanics/molecular mechanics (QM/MM) hybrid approach has been the preferred choice of interest since last decade for modeling reactions in biomolecular systems. The application of QM/MM approach has been expanded right from rescoring the already known complexes and depicting the correct position of some novel molecule to ranking a large number of molecules. It is expected that the application of QM/MM-based scoring will grow in all areas of drug discovery. However, the most promising area will be its application in repositioning, that is, assigning novel functions or targets to the already existing drugs, as this would stop the rising attrition rates as well as reduce the overall time and cost of drug discovery procedure.

Polarization effects on spectra of spherical core/shell nanostructures: Perturbation theory against finite difference approach

Poisson equation is solved analytically in the case of a point charge placed anywhere in a spherical core/shell nanostructure, immersed in aqueous or organic solution or embedded in semiconducting or insulating matrix. Conduction and valence band-edge alignments between core and shell are described by finite height barriers. Influence of polarization charges induced at the surfaces where two adjacent materials meet is taken into account. Original expressions of electrostatic potential created everywhere in the space by a source point charge are derived. Expressions of self-polarization potential describing the interaction of a point charge with its own image–charge are deduced. Contributions of double dielectric constant mismatch to electron and hole ground state energies as well as nanostructure effective gap are calculated via first order perturbation theory and also by finite difference approach. Dependencies of electron, hole and gap energies against core to shell radii ratio are determined in the case of ZnS/CdSe core/shell nanostructure immersed in water or in toluene. It appears that finite difference approach is more efficient than first order perturbation method and that the effect of polarization charge may in no case be neglected as its contribution can reach a significant proportion of the value of nanostructure gap.

Polarization charges effects on optical properties of double ellipsoidal quantum dot

The present study seeks to scrutinize the optical properties of a double ellipsoidal quantum dot (EQD) containing an electron in the presence of a donor impurity. The effect of surface polarization charges due to impurity on absorption coefficients for different values of dielectric constant is investigated. The variational method is used and for different values of ellipticity constant, the linear, nonlinear and total absorption coefficients are calculated as a function of the incident photon energy. The results show that the absorption coefficients of double EQD increase with increases in the ellipticity constant and decrease as polarization charges are considered.

Effect of thermal treatment on magnetic and dielectric response of SrM hexaferrites obtained by hydrothermal synthesis

Electric, dielectric and magnetic properties of SrFe12O19 hexaferrite ceramics obtained from hydrothermally synthesized single-phase nanopowders were studied in wide temperature range. The effect of space charge polarization, related to highly conducting grains with poor conducting grain boundaries, was found to be apparent at high temperatures and at low frequencies. The activation energy of relaxation of the (Fe3+–Fe2+) dipoles in low conducting grain boundary regions was found to amount to 0.20 eV for non-annealed ceramics and to increase to 0.32 eV after thermal treatment. The temperature and frequency dependences of the dielectric permittivity for non-annealed and annealed SrFe12O19 ceramics were found to be correlated with respective dependences of the electric conductivity. We relate the observed increase in the saturation magnetization after annealing to an increase in coherent spin rotation in greater grains, which are however still below the critical single-domain size.

Surface band bending and band alignment of plasma enhanced atomic layer deposited dielectrics on Ga- and N-face gallium nitride

The effects of surface pretreatment, dielectric growth, and post deposition annealing on interface electronic structure and polarization charge compensation of Ga- and N-face bulk GaN were investigated. The cleaning process consisted of an ex-situ wet chemical NH4OH treatment and an in-situ elevated temperature NH3 plasma process to remove carbon contamination, reduce oxygen coverage, and potentially passivate N-vacancy related defects. After the cleaning process, carbon contamination decreased below the x-ray photoemission spectroscopy detection limit, and the oxygen coverage stabilized at ∼1 monolayer on both Ga- and N-face GaN. In addition, Ga- and N-face GaN had an upward band bending of 0.8 ± 0.1 eV and 0.6 ± 0.1 eV, respectively, which suggested the net charge of the surface states and polarization bound charge was similar on Ga- and N-face GaN. Furthermore, three dielectrics (HfO2, Al2O3, and SiO2) were prepared by plasma-enhanced atomic layer deposition on Ga- or N-face GaN and annealed in N2 ambient to investigate the effect of the polarization charge on the interface electronic structure and band offsets. The respective valence band offsets of HfO2, Al2O3, and SiO2 with respect to Ga- and N-face GaN were 1.4 ± 0.1, 2.0 ± 0.1, and 3.2 ± 0.1 eV, regardless of dielectric thickness. The corresponding conduction band offsets were 1.0 ± 0.1, 1.3 ± 0.1, and 2.3 ± 0.1 eV, respectively. Experimental band offset results were consistent with theoretical calculations based on the charge neutrality level model. The trend of band offsets for dielectric/GaN interfaces was related to the band gap and/or the electronic part of the dielectric constant. The effect of polarization charge on band offset was apparently screened by the dielectric-GaN interface states.

Novel laboratory methods for determining the fine scale electrical resistivity structure of core

High-resolution electrical resistivity measurements are made on saturated rocks using novel laboratory instrumentation and multiple electrical voltage measurements involving in principle a four-point electrode measurement but with a single, moving electrode. Flat, rectangular core samples are scanned by varying the electrode position over a range of hundreds of millimetres with an accuracy of a tenth of a millimetre. Two approaches are tested involving a contact electrode and a non-contact electrode arrangement. The first galvanic method uses balanced cycle switching of a floating direct current (DC) source to minimise charge polarisation effects masking the resistivity distribution related to fine scale structure. These contacting electrode measurements are made with high common mode noise rejection via differential amplification with respect to a reference point within the current flow path. A computer based multifunction data acquisition system logs the current through the sample and voltages along equipotentials from which the resistivity measurements are derived. Multiple measurements are combined to create images of the surface resistivity structure, with variable spatial resolution controlled by the electrode spacing. Fine scale sedimentary features and open fractures in saturated rocks are interpreted from the measurements with reference to established relationships between electrical resistivity and porosity. Our results successfully characterise grainfall lamination and sandflow cross-stratification in a brine saturated, dune bedded core sample representative of a southern North Sea reservoir sandstone, studied using the system in constant current, variable voltage mode. In contrast, in a low porosity marble, identification of open fracture porosity against a background very low matrix porosity is achieved using the constant voltage, variable current mode. This new system is limited by the diameter of the electrode that for practical reasons can only be reduced to between 0.5 and 0.75 mm. Improvements to this resolution may be achieved by further reducing the electrode footprint to 0.1 mm × 0.1 mm using a novel high-impedance, non-contact potential probe. Initial results with this non-contact electric potential sensor indicate the possibility for generating images with grain-scale resolution.

Phase-field modeling of switchable diode-like current-voltage characteristics in ferroelectric BaTiO3

A self-consistent model has been proposed to study the switchable current-voltage (I-V) characteristics in Cu/BaTiO3/Cu sandwiched structure combining the phase-field model of ferroelectric domains and diffusion equations for ionic/electronic transport. The electrochemical transport equations and Ginzburg-Landau equations are solved using the Chebyshev collocation algorithm. We considered a single parallel plate capacitor configuration which consists of a single layer BaTiO3 containing a single tetragonal domain orientated normal to the plate electrodes (Cu) and is subject to a sweep of ac bias from −1.0 to 1.0 V at 25 °C. Our simulation clearly shows rectifying I-V response with rectification ratios amount to 102. The diode characteristics are switchable with an even larger rectification ratio after the polarization direction is flipped. The effects of interfacial polarization charge, dopant concentration, and dielectric constant on current responses were investigated. The switchable I-V behavior is attributed to the polarization bound charges that modulate the bulk conduction.

Liquid–Liquid Extraction of Uranyl by TBP: The TBP and Ions Models and Related Interfacial Features Revisited by MD and PMF Simulations

We report a molecular dynamics (MD) study of biphasic systems involved in the liquid-liquid extraction of uranyl nitrate by tri-n-butylphosphate (TBP) to hexane, from "pH neutral" or acidic (3 M nitric acid) aqueous solutions, to assess the model dependence of the surface activity and partitioning of TBP alone, of its UO2(NO3)2(TBP)2 complex, and of UO2(NO3)2 or UO2(2+) uncomplexed. For this purpose, we first compare several electrostatic representations of TBP with regards to its polarity and conformational properties, its interactions with H2O, HNO3, and UO2(NO3)2 species, its relative free energies of solvation in water or oil environments, the properties of the pure TBP liquid and of the pure-TBP/water interface. The free energies of transfer of TBP, UO2(NO3)2, UO2(2+), and the UO2(NO3)2(TBP)2 complex across the water/oil interface are then investigated by potential of mean force (PMF) calculations, comparing different TBP models and two charge models of uranyl nitrate. Describing uranyl and nitrate ions with integer charges (+2 and -1, respectively) is shown to exaggerate the hydrophilicity and surface activity of the UO2(NO3)2(TBP)2 complex. With more appropriate ESP charges, mimicking charge transfer and polarization effects in the UO2(NO3)2 moiety or in the whole complex, the latter is no more surface active. This feature is confirmed by MD, PMF, and mixing-demixing simulations with or without polarization. Furthermore, with ESP charges, pulling the UO2(NO3)2 species to the TBP phase affords the formation of UO2(NO3)2(TBP)2 at the interface, followed by its energetically favorable extraction. The neutral complexes should therefore not accumulate at the interface during the extraction process, but diffuse to the oil phase. A similar feature is found for an UO2(NO3)2(Amide)2 neutral complex with fatty amide extracting ligands, calling for further simulations and experimental studies (e.g., time evolution of the nonlinear spectroscopic signature and of surface tension) on the interfacial landscape upon ion extraction.

Change of the work function of platinum electrodes induced by halide adsorption

The properties of a halogen-covered platinum(111) surface have been studied by using density functional theory (DFT), because halides are often present at electrochemical electrode/electrolyte interfaces. We focused in particular on the halogen-induced work function change as a function of the coverage of fluorine, chlorine, bromine and iodine. For electronegative adsorbates, an adsorption-induced increase of the work function is usually expected, yet we find a decrease of the work function for Cl, Br and I, which is most prominent at a coverage of approximately 0.25 ML. This coverage-dependent behavior can be explained by assuming a combination of charge transfer and polarization effects on the adsorbate layer. The results are contrasted to the adsorption of fluorine on calcium, a system in which a decrease in the work function is also observed despite a large charge transfer to the halogen adatom.

A Comparative Quantum Mechanical Charge Field Study of Uranyl Mono- and Dicarbonate Species in Aqueous Solution

A theoretical study of the structure and dynamics of the uranyl mono- and dicarbonate species in aqueous solution employing the quantum mechanical charge field-molecular dynamics (QMCF-MD) method is presented. The obtained structural and dynamical data were found to be in good agreement with several experimental data and theoretical investigations available in the literature. The five-fold coordination pattern observed for the equatorially bounded ligands of the uranyl ion was found to deviate from the results of a number of previous studies based on quantum chemical cluster calculations and classical molecular dynamics studies, however. The reason for the different description of the system can be seen on the one hand in the capability of QM/MM-type simulations to take charge transfer, polarization, and many-body effects into account, while the presence of a large number of MM solvent molecules ensures that the simulation system mimics the environment in the bulk of a liquid. In addition to pair, three-body and angular distributions, the use of spatial density data enabled a detailed characterization of the three-dimensional arrangement of ligands in the vicinity of the complex. Further analysis of dynamical data such as hydrogen-bond correlation functions and mean lifetime analysis enabled a detailed characterization of the properties of the complexes in aqueous solution. It could be shown that the bulk-oriented oxygen atoms of the carbonate ions form strong hydrogen bonds with bulk molecules, while the tendency of the oxygen atoms of the uranyl(VI) show decreasing tendency to form hydrogen bonds upon complexation.

Effect of dielectric mismatch on impurity binding energy in double ellipsoidal quantum dots

The present study seeks to scrutinize the effect of polarization charges on the electronic properties of double ellipsoidal quantum dots. In this regard, the effective-mass approximation within a variational scheme is used and the binding energy of hydrogenic impurity located at the center of ellipsoidal quantum dot (EQD) is calculated for GaAs/GaAlAs/AlAs structure. The effect of surface polarization charges due to impurity and self-polarization charges on the binding energy is considered. The results showed that the binding energy depends not only on the thickness of the intermediate layer but also on the ellipticity constant.

Molecular dynamics simulations of n-hexane at 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide interface

Molecular dynamics simulations of n-hexane adsorbed onto the interface of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([bmim][Tf2N]) are performed at three n-hexane surface densities, ranged from 0.7 to 2.3 μmol/m(2) at 300 K. For [bmim][Tf2N] room-temperature ionic liquid, we use a non-polarizable all-atom force field with the partial atomic charges based on ab initio calculations for the isolated ion pair. The net charges of the ions are ±0.89e, which mimics the anion to cation charge transfer and polarization effects. The OPLS-AA force field is employed for modeling of n-hexane. The surface tension is computed using the mechanical route and its value decreases with increase of the n-hexane surface density. The [bmim][Tf2N]/n-hexane interface is analyzed using the intrinsic method, and the structural and dynamic properties of the interfacial, sub-interfacial, and central layers are computed. We determine the surface roughness, global and intrinsic density profiles, and orientation ordering of the molecules to describe the structure of the interface. We further compute the survival probability, normal and lateral self-diffusion coefficients, and re-orientation correlation functions to elucidate the effects of n-hexane on dynamics of the cations and anions in the layers.

Enhancement of ionic conductivity in Li2O–SiO2 glass in nanodimensions grown within pellets of ZnO nanorods and magnetodielectric properties of these nanocomposites

23Li2O·77SiO2 glass with nanodimensions was grown within the pores of a pellet formed by ZnO nanorods of a diameter of 70nm and lengths varying from 80nm to 270nm. The resistivity of the nanoglass was less than that of its bulk counterpart by more than three orders of magnitude. The activation energy was found to be 35% lower than that of the bulk glass. This was ascribed to an increase in free volume in the nanodimensional glass. The ac conductivity variation at high frequency showed an exponent of 0.5 indicating two dimensional movements of lithium ions in the nanoglass. Nanocomposites of lithia–silica nanoglass and CuO nanoparticles showed magnetodielectric property with dielectric permittivity at 500kHz decreasing by 5.3% at 2T. This was explained on the basis of space charge polarization and Hall Effect. Nanocomposites of lithia–silica nanoglass and ZnO nanorods exhibited a giant magnetodielectric effect with the dielectric permittivity increasing by 20% to 99% at 2T depending on the measuring frequency. This was also ascribed to space charge polarization with the ZnO nanophase showing a negative magnetoresistance.