Variation Of Charge Density Research Articles

Copper-based photocatalysts with natural organic ligands for efficient removal of tetracycline under visible light

The excessive use of broad-spectrum antibiotics, such as tetracycline, presents a significant challenge to human survival and development. Oxygen vacancies (OVs) metal-organic framework (MOF) materials were synthesized using natural organic acids (L-malic acid, L-aspartic acid, and L-asparagine) with similar structures but different charge densities, along with copper as the metal linking agent. The presence of oxygen vacancies in the catalyst provides abundant active sites for photocatalytic reactions. The employment of flexible straight-chain organic ligands devoid of rigid polycyclic rings, combined with the incorporation of different substituents to induce variations in charge density, the resulting catalysts exhibit distinct photocatalytic activities under visible light. Density functional theory calculations confirm that L-asparagine exhibits the largest electron density difference, and the Cu-based MOF (Cu-ASU) synthesized as an organic ligand exhibits the highest photocatalytic activity under visible light excitation. The catalyst displayed remarkable photocatalytic activity against tetracycline antibiotics under identical conditions (with removal rates of 93.5 % for tetracycline, 81.4 % for terramycin, and 95.6 % for chloramphenicol hydrochloride). This provides a novel approach for the design and synthesis of photocatalysts for the removal of antibiotics from water.

Molecular Dynamics Simulation Study on the Structural and Thermodynamic Analysis of Oxidized and Unoxidized Forms of Polyaniline.

The conducting polymer polyaniline (PANI) has shown significant interest for the development of electrified membranes (EMs) with superior antifouling characteristics. However, the blending and doping of PANI with other polymers and nanomaterials highly influence the properties of the membrane surface. PANI exists in two forms: oxidized, known as emeraldine salt (ES), and unoxidized, referred to as emeraldine base (EB). Therefore, understanding the different forms of PANI and the variations between the oxidized and unoxidized forms along the length of the polymer chain is intriguing. In this paper, we present the design of a novel copolymer consisting of EB and ES monomers with varying charge densities and different segmental arrangements. We present various intra- and intermolecular structural properties of the PANI chains using all-atom molecular dynamics (MD) simulations. Herein, we present a detailed conformational free energy analysis to understand the conformational transitions of the PANI chains. Our results show increased radius of gyration (Rg) values with increased charge density. Furthermore, we also present the H-bonding, free energy analysis, reduced density gradient (RDG), and solvent-accessible surface area (SASA) values for the observed conformational transitions of PANI. Therefore, these observations are crucial in understanding the complex behavior of chains for designing target-specific polymeric materials.

Effect of PCE anionic charge density on fly ash cementitious system-PCE compatibility

In this study, the compatibility of polycarboxylate-based water-reducing admixtures (PCEs) with cementitious systems containing fly ash (FA) was investigated. For this purpose, PCEs with carboxylate, phosphate, and sulfonate anionic groups having different anionic charge densities were synthesized. The effects of PCEs on fresh properties and compressive strength of cementitious systems containing FA were investigated. The PCE with 9% phosphate substitution and high anionic charge density was found to be the most effective, requiring the least amount for the target flow. Similarly, in terms of the PCE requirement for the minimum Marsh funnel flow time and rheological parameters, the best performance was obtained with 5% sulfonate substituted PCE having high anionic charge density. While FA had a positive effect on the PCE requirement and consistency retention of the mixtures; it had a negative effect on Marsh funnel flow time, rheological properties, and compressive strength. However, the rheological properties of the mortar mixtures were not adversely affected by the FA substitution as much as that of the paste mixtures. Regarding the 28-day compressive strength of mortar mixtures, the optimum FA substitution ratio was 15%. Fly ash substitution above this level reduced the compressive strength at all ages including 28-day strength. Anionic charge density variation of PCE had no significant influence on the compressive strength of the mortars.

Degradation mechanism of SiC diodes under thermal and irradiation stress

Abstract Silicon carbide (SiC)-based diodes are widely used due to their high temperature resistance. In this paper, breakdown voltage of 4H-SiC JBS diodes and capacitance-voltage of 4H-SiC MOS capacitors with identical interfacial structure were both measured at high temperature to study their interfacial properties. By analyzing the variation of interfacial properties, the correlation between thermal stress and failure mode of 4H-SiC JBS diodes was further established to reveal their degradation mechanism. During initial high temperature storage, interfacial negative effective charge density of 4H-SiC JBS diodes may increase, leading to the decrease of breakdown voltage. As storage time increases, interfacial charge density began reducing, resulting in the increase of breakdown voltage. Avalanche luminescence verifies that the variation of interfacial charge density under thermal stress led to the degradation of 4H-SiC JBS diodes and further affected their breakdown voltage. Finally, degradation mechanism of SiC-JBS, SiC-SBD and SiC-PIN diodes under irradiation stress was investigated. After irradiation, forward current of some SiC diodes increased at a small forward voltage. However, the reverse characteristics deteriorated obviously and even failed.

Engineering the Electrostatic Interactions between Oppositely Charged Polymer-Grafted Nanoparticles for Constructing Colloid Molecules on Substrates.

Arrays of nanoparticle (NP) clusters with controlled architectures show broad applications in nanolasers, sensors, and photocatalysis, but the fabrication of these arrays on substrates remains a grand challenge. This review presents a highly effective polymer-based strategy for the process-directed self-assembly of binary polyelectrolyte-grafted NPs (PGNPs) bearing opposite charges into stable colloidal molecules (CMs) on substrates via electrostatic interactions. The coordination number (x) of ABx CMs can be tuned by adjusting the pH or ionic strength of the solution or by employing different combinations of PGNPs with varying charge densities. Large-area CMs with diverse structures ranging from AB to AB7 can be constructed on substrates in high yields. This approach is applicable to PGNPs with different cores of NPs. This assembly strategy offers a useful tool for the fabrication of structurally precise assemblies on substrates with broad applications.

Measurement of space charge density distributions and dielectric resonance enhancement of beam deflection properties of KTN crystal

In recent years, potassium tantalum niobate (KTN) electro-optical deflection devices have gained considerable attention because of their notable advantages, such as large deflection angles, low operational voltage requirements, and compact dimensions. This study uses the phase-shifted interferometric optical path to characterize the influence of direct current (DC) voltage on charge density. An interferogram is acquired using the four-step phase-shifting technique, enabling the calculation of phase delays and deducing the variation in charge density. Experimental results demonstrate that the charge density near the cathode increases with an increase in DC voltage. Subsequently, we utilize the frequency dependence of the dielectric constant of the KTN crystal on the electric field. The dielectric constant can be enhanced when the characteristic frequency of the motion of the polar nanoscale region matches the frequency of the electric field. This field-induced enhancement effect improves the beam deflection performance of the KTN crystal. Application requirements in the field of high-speed random scanning can be realized through the mechanism of the KTN crystal co-acting with DC and alternating current electric fields.

Modulation of Electrokinetic Potentials Using Graphene-Based Surfaces and Variable Substrate Charge Density.

Enhanced electrokinetic phenomena, manifested through the observation of a large streaming potential (Vs), were obtained in microchannels with single-layer graphene (SLG)-coated and few-layer graphene (FLG)-coated surfaces. In comparison to silicon microchannels, the Vs obtained for a given pressure difference along the channel (ΔP) was higher by 75% for the graphene-based channels, with larger values in the SLG case. Computational modeling was used to correlate the surface charge density, tuned through plasma processing, and related zeta potential to measured Vs. The implications related to deploying lower dimensional material surfaces for modulating electrokinetic flows were investigated.

Investigation of sheath structure in surface flashover induced by high-power microwave

Flashover is a major limiting factor for the transmission and miniaturization of high-power microwave (HPM) devices. We conducted a study to investigate the developmental process of surface flashover on HPM dielectric windows through particle-in-cell-Monte Carlo collision simulations. A one-dimensional spatial distribution and three-dimensional velocity distribution model is established, encompassing the entire process of surface flashover, which includes electrode field emission, single-surface multipactor, outgassing, and gas breakdown. The nonuniform mesh generation method is employed to enhance the simulation accuracy. The growth rates of electron and ion densities increase as gas pressure rises. Additionally, the discharge transitions gradually from multipactor to gas ionization dominance. Notably, a space-charge-limited (SCL)-like sheath occasionally forms during an rf cycle near the surface under intermediate background pressure (∼0.05 Torr). The SCL-like sheath cannot exist stably. Instead, it periodically disappears and appears as the rf electric field changes. The underlying physics are explained by the variations of the rf electric field, which lead to the variations in the surface charge density, thereby affecting the normal electric field. The normal electric field interacts with the spatial distribution of charged particles, ultimately leading to the formation of the SCL-like sheath. This work may facilitate a comprehensive understanding of the developmental processes of surface flashover.

High-Selectivity-Based Novel Split-Gate VTFET Biosensor for Identification of SARS-CoV-2

The World Health Organization (WHO) has officially declared the international outbreak of severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2), often known as Coronavirus Disease 2019 (COVID-19), a global pandemic based on the significant and sudden increase in human infections worldwide. With suitable treatment and early diagnosis, this outbreak can be controlled to a certain extent. In the present research, the performance of a novel dielectrically modulated heterojunction-based splitgate double cavity vertical TFET biosensor for detecting SARS-CoV-2 with reference to the virus spike, DNA and envelope proteins has been thoroughly investigated. The suggested sensor’s sensitivity has been evaluated through the computation of the deviation in drain current. We model the hybridized biomolecules in the nanogaps as the dielectric constant equivalent of the viral proteins. Additionally, sensing speed and selectivity analysis pertaining to the various biomolecules are also investigated. The proposed sensor exhibits a notably high sensitivity (on the order of 108), high sensing speed, and high selectivity (on the order of 106), indicating its potential as a superior sensor. This study also examines the influence of variations in DNA charge density on the performance of the device. Ultimately, the proposed sensor is evaluated in comparison to its sensitivity and selectivity of a variety of FET-based biosensors previously documented in the literature.

A NUMERICAL ANALYSIS ON THE SUBMICRON- AND MICRON-SIZED PARTICLE SEDIMENTATION IN A WIRE-TO-PLATE ELECTROSTATIC PRECIPITATOR

Electrostatic precipitators (ESPs) are frequently utilized in collecting fine organic and inorganic materials from continuous liquid with few moving parts and high efficiency using electrically charging the particles. In this study, cross-sectional 2D geometry of a wire-to-plate electrostatic precipitator the parametric data of which originally published elsewhere was numerically modeled and validated to investigate submicron-micron particle charging in terms of diffusion and field charging mechanisms and precipitation behavior of particles with detailed electric field properties. Electric field, gas flow, and particle trajectory equations are coupled and solved in a multiphysics solver. Particle tracking is realized with the Lagrangian approach. Results indicate variations in electric field strength and space charge density between corona electrodes, with space charge present in the entire precipitation channel. Between two different charging mechanisms, diffusion charging prevails for charge accumulated on submicron particles, whereas field charging becomes dominant for particles larger than 1μm diameter. However, for the ESP configuration considered in this study, particles reach a charge saturation in less than 0.7 seconds, regardless of their size. Although calculated precipitation efficiencies for micron-sized particles can reach to 100%, efficiencies for submicron particle range drop with increasing particle size, as diffusion charging rapidly loses its effectiveness, in 50-250nm range.

Influence of the liquid ionic strength on the resonance frequency and estimated shell parameters of lipid-coated microbubbles

Measurement of the resonance frequency and shell properties of coated microbubbles (MBs) is important in understanding and optimizing their response to ultrasound. In many applications MBs are in ionic liquids; however, the influence of the medium charges on the MB behavior is not well investigated. This study aims to measure the medium charge interactions with MBs by measuring the frequency-dependent attenuation of the same size MBs in mediums of varying charge density. In-house lipid-coated MBs were size isolated to a mean size of 2.35 μm using differential centrifugation. MBs were suspended in distilled water (DW), Phosphate-Buffered Saline solution (PBS1×) and PBS10×. The frequency-dependent attenuation of the MBs solutions was measured using a system of two aligned 100% bandwidth transducers with 10 MHz center frequency. The MB shell properties were estimated by fitting the linear equation to experiments. With increasing salinity, the frequency of the peak attenuation decreased (13, 7.5 and 6.25 MHz in DW, PBS1× and PBS-10×, respectively) and attenuation peak increased (∼140%). Estimated MBs shell elasticity decreased by 64% between DW and PBS-1× and 36% between PBS-1x and PBS-10x. The estimated shell viscosity reduced by ∼40% between DW and PBS-1× and 42% between PBS-1× and PBS-10×. The significant reduction in the fitted stiffness and viscosity is possibly due to the formation of a densely charged layer around the shell and requires proper inclusion in the related MB models.

Janus molybdenum di-chalcogenides based van der Waals bilayers for supercapacitor electrode design- effects of interlayer stacking orientations on quantum capacitance

In this work, for the first time, the quantum capacitance of an artificial two-dimensional (2D) material system based on van der Waals (vdW) bilayer heterostructures of Janus Molybdenum Di-chalcogenides, MoXY (X≠Y, X/YS, Se, Te) have been extensively investigated for electrode design of electrical double-layer (EDL) supercapacitor. The effects of different interlayer stacking orientations on local charge distribution, interlayer charge transfer, energy band structure, and density of states (DOS) have been comprehensively analyzed and correlated with the excess charge density and quantum capacitance variation with local electrode potential. Furthermore, the total capacitance reduction with respect to EDL capacitance has been analyzed over a wide range of EDL capacitance, and the performance of vdW Janus bilayers has been systematically benchmarked against the natural monolayers/bilayers and Janus monolayers of Molybdenum Di-chalcogenides. The results demonstrate that the large interlayer charge transfer induced built-in interlayer electric field significantly reduces the energy band gap of vdW Janus bilayers for S–Te and Se–Te interlayer stacking, thus leading to a significantly superior quantum capacitance. Finally, the favorable valley-dependent effective mass and band-degeneracy in MoSTe/MoSeTe have greatly enhanced quantum capacitance in S–Te and Se–Te stacking, rendering these bilayers a highly attractive candidate for supercapacitor electrode design.

C, Ge-doped h-BN quantum dot for nano-optoelectronic applications

Emerging materials, particularly nanomaterials, constitute an enduring focal point of scientific inquiry, with quantum dots being of particular interest. This investigation is centered on elucidating the exceptional structural, electromagnetic, and optical characteristics of hexagonal boron nitride (h-BN) quantum dots and h-BN quantum dots doped with carbon (C) and germanium (Ge). The employed methodology in this study hinges on density functional theory coupled with the Vienna Ab initio simulation package. The outcomes of this research unveil the structural stability of hexagonal honeycomb structures upon optimization. Comprehensive examinations encompassing structural properties, electromagnetic characteristics, and charge density variations have been systematically conducted. Furthermore, this work delves into the elucidation of multi-orbital hybridizations that give rise to σ bonds and π bonds. Notably, the outcomes of the optical property analysis divulge intriguing observations. Specifically, the absorption coefficient exhibits zero values within select energy ranges within the visible light spectrum, a phenomenon observed in both pristine and C-doped configurations. This discovery underscores the material’s optical transparency at these specific radiation energies. Additionally, the 0x and 0y components of the dielectric function display negative values across particular energy ranges, a characteristic that holds significant promise for potential applications in nanotechnology communications, offering minimal energy loss.

A novel ventriculoperitoneal shunt flow sensor based on electrically induced spatial variation in cerebrospinal fluid charge density.

Introduction: Ventriculoperitoneal (VP) shunts divert cerebrospinal fluid (CSF) out of cerebral ventricles in patients with hydrocephalus or elevated intracranial pressure (ICP). Despite high failure rates, there exist limited clinically viable solutions for long-term and continuous outpatient monitoring of CSF flow rate through VP shunts. We present a novel, low-power method for sensing analog CSF flow rate through a VP shunt premised on induced spatial electrical charge variation. Methods: Two geometric variants of the proposed sensing mechanism were prototyped: linear wire (P1) and cylindrical (P2) electrodes. Normal saline was gravity-driven through P1 and a commercially available shunt system in series. True flow rates were measured using a high-precision analytical balance. Subsequently, artificial CSF was driven by a programmable syringe pump through P2. Flow rate prediction models were empirically derived and tested. Sensor response was also assessed during simulated obstruction trials. Finally, power consumption per flow measurement was measured. Results: P1 (17mm long) and P2 (22mm long) averaged 7.2% and 4.2% error, respectively, in flow rate measurement from 0.01 to 0.90mL/min. Response curves exhibited an appreciably flattened profile during obstruction trials compared to non-obstructed states. P2 consumed 37.5 µJoules per flow measurement. Conclusion: We propose a novel method for accurately sensing CSF flow rate through a VP shunt and validate this method at the benchtop with normal saline and artificial CSF over a board range of flows (0.01-0.90mL/min). The sensing element is highly power efficient, compact, insertable into existing shunt and valve assemblies, and does not alter CSF flow mechanics.

Charge density fluctuation determined the interlayer friction in bilayer MN4 (M = Be, Mg, and Pt).

MN4 (M = Be, Mg, and Pt) represents a new class of van der Waals materials. These materials are characterized by exceptional electrical and thermal conductivities, remarkable intralayer mechanical strength, and weak interlayer interactions, making them prone to shearing and slipping. Therefore, MN4 has significant potential applications as a solid lubricant. However, until now, there have been only limited comprehensive theoretical investigations focusing on the frictional properties of MN4 systems. Here, the frictional performances of MN4 are systematically analyzed by applying first-principles high-throughput calculations. The results reveal that interlayer friction of MN4 decreases from MgN4 to BeN4 and then to PtN4. The friction is directly determined by charge density variations during the sliding processes. The periodic formation and breaking of quasi-σ bonds in bilayer MgN4 leads to substantial variations in charge density and large interlayer friction. In contrast, the weak charge density alternations in PtN4 lead to rather low frictions in PtN4. Moreover, surface functionalization effectively diminishes friction within bilayer MgN4, but amplifies interlayer friction within bilayer PtN4, and under surface functionalization interlayer friction can be efficiently modulated by out-of-plane polarizations. Interestingly, HBr-MgN4 exhibits two orders of magnitude lower COF compared to intrinsic bilayer MgN4, leading to a phenomenon resembling superlubricity. These results significantly contribute to our understanding of the friction properties, offering valuable guidance for the practical implementation of MN4 in solid lubricants.

Generation of skyrmions by combining thermal and spin-orbit torque: breaking half skyrmions into skyrmions.

Skyrmions, swirling spin textures with topologically protected stability and low critical driven-current density, can be generated from the stripe domain with current pulses, bringing them closer to practical applications in racetrack memory. However, the mechanism of this topological transition from the stripe domain to the skyrmion remains unclear because the transition process occurs at a nanosecond timescale, giving rise to difficulties in observing this process using imaging tools. In this study, we controlled the domain wall - skyrmion transition by combining Joule heating with spin-orbit torque (SOT) and experimentally observed the details of this process, by which we confirmed the mechanism: the spatial variation of the topological charge density induces half skyrmions branching from the stripe domains, and these half skyrmions overcome the surface tension and break away from the stripe domain, resulting in the generation of skyrmions. The details were observed by employing Joule heating to overcome the pinning effect and manipulating the strength of the SOT to induce the branching and breaking of half skyrmions. These findings offer new insights into skyrmion generation and serve as an important step towards the development of highly efficient devices for processing and computing based on skyrmionics.

Structural dependence of concentrated skim milk curd on micellar restructuring

This study was conducted to establish an understanding of how milk concentration modulates the rennet curd structure. Rennet-induced gelation and renneting under slow acidification achieved using glucono-δ-lactone (GDL) and structural properties of reconstituted skim milk gels at two concentration levels (9 and 25 % total solids) were studied by measuring variations in (a) viscoelastic behaviour, (b) micellar size, charge density, diffusivity, and (c) hydrophobicity using dynamic rheometry, dynamic light scattering and fluorimetry, respectively. Concentrated milk showed a greater estimated hydrodynamic radius of casein micelles, lower zeta (ζ)-potential, ratio of serum to total Calcium (Ca) and charge density and increased surface hydrophobicity, all supporting the view that micellar restructuring particularly sub-particle transfer takes place and contributes to rapid gelation. Moreover, hydrophobic interactions occurred very quickly (within 5 min in combined gels, 10 min for renneting only), demonstrating their pivotal role during the flocculation stage. All gels exhibited a solid viscoelastic character as the elastic modulus (G′) was greater than loss modulus (G″) while both G′ and tan δ (G''/G′) were frequency-dependent. Frequency sweeps classified the concentrated gels into three stiffness categories caused by the level of rennet or GDL as rigid, hard and soft, whereas an increased flow-like behaviour (high tan δ), restricted diffusion and excessive water retention revealed limited structural rearrangements (contraction & macrosyneresis) during curd ageing. Acidification increased the diffusion rate in control curd, thus, enhanced contractive rearrangements, macrosyneresis and curd strength. Findings suggest that micellar restructuring induced by milk concentration is the principal modulator of the curd structure.

Impact of hybrid natural deep eutectic solvent and polyacrylamide flocculant systems on the flocculation of highly stable graphene oxide suspensions

Graphene oxide (GO)-based nanomaterials have garnered significant attentions for various industrial applications due to their remarkable structural and physicochemical properties. Consequently, the impact of the increased discharge of GO into the environment also becomes a matter of significant concern due to the toxicity of GO nanoparticles to human health and the ecosystem. Therefore, efficient removal of GO from wastewaters before discharge into water bodies is crucial and remains a critical challenge in wastewater treatment due to the formation of highly stable GO suspensions in aqueous media. Accordingly, this work investigates the flocculation of aqueous GO suspensions using a range of single and hybrid coagulant/flocculant systems comprising a choline chloride-based natural deep eutectic solvent (NADES) coagulant and commercial high-molecular-weight polyacrylamide (PAM) based flocculants with variable surface charge densities. The effect of variations in the coagulant/flocculant charge type, charge density, and dosage on GO deflocculation was examined using residual turbidity, zeta potential, and floc size measurements. Cationic PAMs demonstrated the best performance among single flocculant systems with GO removal efficiency exceeding 97% and compact settleable flocs (D50 > 20 µm) at optimum doses in the range of 15–20 mg/L. The high charge density of FO 4800 SH further enhanced the GO removal efficiency by 1.1% and reduced the required optimum dose by 5 mg/L compared to FO 4350 SH. Hybrid flocculant systems revealed that anionic PAMs are the best performing flocculants when utilized with a fixed concentration of NADES coagulant. High GO removal efficiencies exceeding 98%, maximum zeta potential reduction, and the formation of large flocs (D50 > 20 µm) were achieved. The low charge density variant AN 923 SH offered better flocculation conditions by reducing the optimum PAM dose required by 5 mg/L compared to AN 956 SH. The NADES/AN 923 SH hybrid system was determined to be the optimal combination for a highly efficient treatment of GO suspensions at a fixed NADES dose of 0.048 M and a low optimum PAM dose of 5 mg/L that resulted in a GO removal efficiency of 98.1%, turbidity of 2.5 NTU, zeta potential of − 3.7 mV, and a mean D50 floc size of 26.1 µm.

Electrochemically Induced Breakdown of Integrated Microsupercapacitors Based on Lipon

Lithium Phosphorous Oxynitride (LiPON) solid electrolyte has gathered a lot of attention due to its favorable ionic conductivity (10-6 Scm-1), good electronic insulation (10-14 Scm-1) and electrochemical stability[1]. Solid state microsupercapacitors based on LiPON have been demonstrated to meet demanding performances required for novel on-chip technologies[2,3]. The electric double layer (EDL) formation at the electrode interface results in the high capacitance and energy density of these devices. The EDL and to an extent the bulk of the electrolyte layer will be affected by the electric potential/field present during the operation. In this work, the electrochemical breakdown of microsupercapacitors were studied under different bias conditions. The influence of device geometry and test conditions on failure of LiPON based devices will provide the scope for potential applications as well.PVD depositions of thin LiPON films in MIM structure (20nm ,50nm,100nm) were fabricated for the study with Pt bottom electrode and Ti/TiN top electrodes. The devices were electrically characterised by Impedance spectroscopy and subjected to a voltage sweep from 0 to ±19V at various scan rates. LiPON was found to undergo electrochemical degradation followed by electrical breakdown as previously reported elsewhere[1]. Increasing the scan rate and thickness of LiPON, increased the breakdown voltage of LiPON. The electrode material influenced the degradation and the interface was found to evolve with successive voltage levels. The interface was found to drive the degradation using equivalent circuit analysis of Impedance spectroscopy results. Charge densities extracted for breakdown indicate possible electronic conduction and Li depletion, which were further verified with physico-chemical characterisation. A model of capacitive and resistive elements will be discussed to capture the individual contributions for electrochemically driven failure and thereby identify the parameters to tune or delay such mechanisms.This work identifies various factors which could modify electrochemical breakdown behaviour of LiPON. The modification of electrochemical breakdown voltage/strength and variation in charge density with scan rate has been newly identified. Further, resolving various contributions to different circuit elements will provide a way to understand and decorrelate their role in electrochemical breakdown.

Nonequilibrium Ab Initio Molecular Dynamics Simulation of Water Splitting at Fe2O3-Hematite/Water Interfaces in an External Electric Field.

In the exploration of the optimal material for achieving the photoelectrochemical dissociation of water into hydrogen, hematite (α-Fe2O3) emerges as a highly promising candidate for proof-of-concept demonstrations. Recent studies suggest that the concurrent application of external electric fields could enhance the photoelectrochemical (PEC) process. To delve into this, we conducted nonequilibrium ab initio molecular dynamics (NE-AIMD) simulations in this study, focusing on hematite-water interfaces at room temperature under progressively stronger electric fields. Our findings reveal intriguing evidence of water molecule adsorption and dissociation, as evidenced by an analysis of the structural properties of the hydrated layered surface of the hematite-water interface. Additionally, we scrutinized intermolecular structures using radial distribution functions (RDFs) to explore the interaction between the hematite slab and water. Notably, the presence of a Grotthuss hopping mechanism became apparent as the electric field strength increased. A comprehensive discussion based on intramolecular geometry highlighted aspects such as hydrogen-bond lengths, H-bond angles, average H-bond numbers, and the observed correlation existing among the hydrogen-bond strength, bond-dissociation energy, and H-bond lifetime. Furthermore, we assessed the impact of electric fields on the librational, bending, and stretching modes of hydrogen atoms in water by calculating the vibrational density of states (VDOS). This analysis revealed distinct field effects for the three characteristic band modes, both in the bulk region and at the hematite-water interface. We also evaluated the charge density of active elements at the aqueous hematite surface, delving into field-induced electronic charge-density variations through the Hirshfeld charge density analysis of atomic elements. Throughout this work, we drew clear distinctions between parallel and antiparallel field alignments at the hematite-water interface, aiming to elucidate crucial differences in local behavior for each surface direction of the hematite-water interface.