Electric Field Gradient Research Articles

Assessment of Approximations to the Embedding Potential in Frozen-Density Embedding Theory for the Calculation of Electric Field Gradients.

The approximations to the embedding potential in frozen-density embedding theory (FDET) have been assessed for the first time for the calculation of the electric field gradient (EFG) at a nucleus. FDET-based methods using a hierarchy of approximations are applied to evaluate the EFG at the nuclei of an HCl molecule in several noncovalently bound clusters chosen to represent potential liquid or molecular crystal systems. A detailed assessment of such approximations is made for the Hartree-Fock treatment of electron-electron correlation (both in FDET and in the reference calculations for the whole cluster). The emerging choice of the optimal set of approximations is reconfirmed in calculations in which electron-electron calculations are treated at the MP2 level. Our optimized protocol produces average errors in the complexation-induced EFG shift on the order of 25% relative to conventional quantum mechanical calculations for the whole cluster. This protocol is shown to be numerically robust and leads to enormous computational savings compared to a complete quantum mechanical treatment of the embedded species and its environment. For a cluster comprising a Na+ cation and up to 24 water molecules, the computation time is reduced by a factor of 30,000 at the expense of introducing an error in the environment-induced EFG shift of 22%.

Predicting 51V nuclear magnetic resonance observables in molecular crystals.

Solid-state nuclear magnetic resonance (NMR) spectroscopy and quantum chemical density functional theory (DFT) calculations are widely used to characterize vanadium centers in biological and pharmaceutically relevant compounds. Several techniques have been recently developed to improve the accuracy of predicted NMR parameters obtained from DFT. Fragment-based and planewave-corrected methods employing hybrid density functionals are particularly effective tools for solid-state applications. A recent benchmark study involving molecular crystal compounds found that fragment-based NMR calculations using hybrid density functionals improve the accuracy of predicted 51V chemical shieldings by 20% relative to traditional planewave methods. This work extends the previous study, including a careful analysis of 51V chemical shift anisotropy, electric field gradient calculations, and a more extensive test set. The accuracy of planewave-corrected techniques and recently developed fragment-based methods using electrostatic embedding based on the polarized continuum model (PCM) are found to be highly competitive with previous methods. Planewave-corrected methods achieve a 34% improvement in the errors of predicted 51V chemical shieldings relative to planewave. Additionally, planewave-corrected and fragment-based calculations were performed using PCM embedding, improving the accuracy of predicted 51V chemical shielding (CS) tensor principal values by 30% and values by 15% relative to traditional planewave methods. The performance of these methods is further examined using a redox-active oxovandium complex and a common 51V NMR reference compound.

Drop That Activation Energy: Tetragonal to Cubic Transformations in Na3PS4−xSex for Solid State Sodium Ion Battery Materials

AbstractSodium‐containing chalcogenide materials are emerging as a class of solid electrolytes for application in inexpensive all‐solid‐state sodium‐ion batteries due to their high ionic conductivity, abundance, and degree of synthetic and structural variability. Members of the solid solution Na3PS4−xSex, which are promising solid electrolytes for sodium‐ion batteries, are prepared by reaction at high temperature. With increasing substitution of S by Se, the structure transforms from tetragonal (space group P21c for x = 0, 1) to cubic (space group I3m for x = 2, 3, 4). Within the solid solution, the S and Se atoms are completely disordered in the environments around the P atoms, in accordance with a binomial distribution, as inferred by the 31P nuclear magnetic resonance (NMR) spectra. In 23Na NMR experiments conducted at different magnetic fields and temperatures, quadrupolar lineshapes are observed that are influenced by sodium ion dynamics; the activation energies decrease from 0.21 to 0.15 eV on progressing from the S‐ to the Se‐rich members. A dynamic model is proposed to account for the changes in the 23Na quadrupolar lineshapes by switching the orientations of the electric field gradient and chemical shift anisotropy tensors when Na+ ions hop to the four nearest Na sites.

Rapidly determining the 3D structure of proteins by surface-enhanced Raman spectroscopy.

Despite great advances in protein structure analysis, label-free and ultrasensitive methods to obtain the natural and dynamic three-dimensional (3D) structures are still urgently needed. Surface-enhanced Raman spectroscopy (SERS) can be a good candidate, whereas the complexity originated from the interactions between the protein and the gradient surface electric field makes it extremely challenging to determine the protein structure. Here, we propose a deciphering strategy for accurate determination of 3D protein structure from experimental SERS spectra in seconds by simply summing SERS spectra of isolated amino acids in electric fields of different strength with their orientations in protein. The 3D protein structure can be reconstructed by comparing the experimental spectra obtained in a well-defined gap-mode SERS configuration with the simulated spectra. The gradient electric field endows SERS with a unique advantage to section biomolecules with atomic precision, which makes SERS a competent tool for monitoring biomolecular events under physiological conditions.

Intramolecular Donor–Acceptor Design in Porous Organic Framework for Liquid Fuels Adsorption Desulfurization

AbstractA porous organic framework containing well‐defined donor–acceptor units, named donor–acceptor porous organic framework (D–A‐POF), is successfully synthesized. The localized electric field gradient at the pore surface induced by the intramolecular donor–acceptor (D–A) interactions endows D–A‐POF with excellent desulfurization capabilities. D–A‐POF exhibits high adsorption capacity of 3‐methylthiophene (12.26 mmol g−1, 392.32 mg S g−1) and 1‐benzothiophene (793.65 mg g−1, 189.25 mg S g−1) with impressive adsorption selectivity. Density functional theory calculations provide compelling evidence of the preferential selective adsorption of aromatic thiophene sulfides in D–A‐POF. In fixed‐bed breakthrough experiments, D–A‐POF demonstrates its ability to selectively capture thiophene sulfides from model gasoline, resulting in fuel with sulfide content below 10 ppb. The high stability and high desulfurization efficiency of D–A‐POF make it promising as a new porous adsorbent for ultra‐depth adsorption desulfurization.

An Intensity Tensor and Electric Field Gradient Tensor for Fe3+ at M1 Sites of Aegirine–Augite Using Single-Crystal Mössbauer Spectroscopy

An intensity tensor of quadrupole doublets and an electric field gradient tensor for Fe3+ at M1 sites in aegirine–augite ((Ca0.16Na0.86)∑1.02(Mg0.13Fe2+0.04Fe3+0.72 Al0.07)∑0.96Si2.01O6) are determined using single-crystal Mössbauer spectroscopy. The components of the intensity tensor are IXX = 0.670 (19), IYY = 0.353 (14), IXY = −0.113 (37) and IZZ = 0.477 (33). The components of the electric field gradient tensor (VXX, VYY and VZZ) for Fe3+ at M1 sites in aegirine–augite are −5.96 × 109, −4.65 × 1010 and 5.23 × 1010 C/m3, respectively. Comparisons of the intensity tensor of aegirine–augite with those of aegirine and augite (Wo40En45Fs16) that have already been reported and the IXX, IYY, IXY and IZZ intensity tensor components of aegirine–augite in this study are almost the same as those of aegirine, but different from those of augite. While the M2 sites of aegirine–augite and aegirine are fully occupied with Na+ and Ca2+ ions, the M2 sites of augite are not fully occupied with Ca2+. The compositional dependency of the intensity tensor components suggests that the intensity tensor components for Fe3+ at the M1 site of a solid solution between aegirine and augite are dependent on the occupancy of large cations such as Ca2+ and Na+ at M2 sites.

Cobalt-59 NMR relaxation times of symmetric tris(γ-substituted-acetylacetonato)cobalt(III) complexes in benzene

Cobalt-59 NMR relaxation times, T1(59Co), and chemical shifts, δ(59Co), of symmetric tris(γ-substituted-acetylacetonato)cobalt(III) complexes, [Co(acac-X)3], which have chloride, bromide, nitro, and phenyl groups at the methine carbon atoms in the chelate ligands, have been measured in benzene at four temperatures between 284 and 319 K. In view of the viscosity dependence of 1/T1(59Co), the 59Co relaxation is caused by the reorientation of the static electric field gradient at the nucleus in every complex. Assuming that the rotational volume is replaced by the van der Waals volume, the nuclear quadrupolar coupling products, {(1 + ηq2/3)(eQq/h)2}1/2, were obtained for the series of [Co(acac-X)3] complexes in benzene. The negative correlation between {(1 + ηq2/3)(eQq/h)2}1/2 and δ(59Co) was observed for the four complexes [Co(acac)3], [Co(acac-Cl)3], [Co(acac-Br)3], and [Co(acac-NO2)3] except for [Co(acac-Ph)3]. This discrepancy strongly suggests that the rotational volume of the propeller-like [Co(acac-Ph)3] complex with the protruding phenyl groups cannot be simply treated as the van der Waals volume, different from the other almost spherical complexes. Actually, the estimation of the rotational volumes from the distances between the central cobalt and g-substituents gave much better correlation between {(1 + ηq2/3)(eQq/h)2}1/2 and δ(59Co) for all the complexes including [Co(acac-Ph)3].

Electrical stimulation via repeated biphasic conducting materials for peripheral nerve regeneration

Improved materials for peripheral nerve repair are needed for the advancement of new surgical techniques in fields spanning from oncology to trauma. In this study, we developed bioresorbable materials capable of producing repeated electric field gradients spaced 600 μm apart to assess the impact on neuronal cell growth, and migration. Electrically conductive, biphasic composites comprised of poly (glycerol) sebacate acrylate (PGSA) alone, and doped with poly (pyrrole) (PPy), were prepared to create alternating segments with high and low electrically conductivity. Conductivity measurements demonstrated that 0.05% PPy added to PSA achieved an optimal value of 1.25 × 10−4 S/cm, for subsequent electrical stimulation. Tensile testing and degradation of PPy doped and undoped PGSA determined that 35–40% acrylation of PGSA matched nerve mechanical properties. Both fibroblast and neuronal cells thrived when cultured upon the composite. Biphasic PGSA/PPy sheets seeded with neuronal cells stimulated for with 3 V, 20 Hz demonstrated a 5x cell increase with 1 day of stimulation and up to a 10x cell increase with 3 days stimulation compared to non-stimulated composites. Tubular conduits composed of repeated high and low conductivity materials suitable for implantation in the rat sciatic nerve model for nerve repair were evaluated in vivo and were superior to silicone conduits. These results suggest that biphasic conducting conduits capable of maintaining mechanical properties without inducing compression injuries while generating repeated electric fields are a promising tool for acceleration of peripheral nerve repair to previously untreatable patients.Graphical

Can simple 'molecular' corrections outperform projector augmented-wave density functional theory in the prediction of 35 Cl electric field gradient tensor parameters for chlorine-containing crystalline systems?

Many-body expansion (MBE) fragment approaches have been applied to accurately compute nuclear magnetic resonance (NMR) parameters in crystalline systems. Recent examples demonstrate that electric field gradient (EFG) tensor parameters can be accurately calculated for 14 N and 17 O. A key additional development is the simple molecular correction (SMC) approach, which uses two one-body fragment (i.e., isolated molecule) calculations to adjust NMR parameter values established using 'benchmark' projector augmented-wave (PAW) density functional theory (DFT) values. Here, we apply a SMC using the hybrid PBE0 exchange-correlation (XC) functional to see if this can improve the accuracy of calculated 35 Cl EFG tensor parameters. We selected eight organic and two inorganic crystal structures and considered 15 chlorine sites. We find that this SMC improves the accuracy of computed values for both the 35 Cl quadrupolar coupling constant (CQ ) and the asymmetry parameter ( ) by approximately 30% compared with benchmark PAW DFT values. We also assessed a SMC that offers local improvements not only in terms of the quality of the XC functional but simultaneously in the quality of the description of relativistic effects via the inclusion of spin-orbit effects. As the inorganic systems considered contain heavy atoms bonded to the chlorine atoms, we find further improvements in the accuracy of calculated 35 Cl EFG tensor parameters when both a hybrid functional and spin-orbit effects are included in the SMC. On the contrary, for chlorine-containing organics, the inclusion of spin-orbit relativistic effects using a SMC does not improve the accuracy of computed 35 Cl EFG tensor parameters.

A three-dimensional collocation finite element method for higher-order electromechanical coupling

Flexoelectricity is a fundamental property found in all nano/micro-scale dielectric materials, even those with centrosymmetry. It describes coupling between electric field and nonuniform mechanical strains, as well as between electric field gradient and mechanical strains. This work presents a three-dimensional second-order collocation finite element method, which can model higher-order electromechanical coupling and is computationally efficient. The formulations for the 27-noded mixed finite element based on the collocation principle are derived and translated into Fortran code. Additionally, a 27-noded element mesh generating script is developed. The new finite element is validated by simulating various boundary value problems and comparing the outcomes with known 2D and 3D results, showing a good agreement. The developed finite element can be used for computationally efficient simulations of the complex electromechanical structures including flexoelectricity.

Electrostatic Contribution to 19F Chemical Shifts in Fluorotryptophans in Proteins.

DFT calculations indicate that the 19F chemical shifts of aromatic rings containing single fluorine substituents are sensitive to the electric fields and electric field gradients at the position of the fluorine atom. The present work explores whether long-range structure restraints can be gained from changes in 19F chemical shifts following mutations of charged to uncharged residues. 19F chemical shifts of fluorotryptophan residues were measured in two different proteins, GB1 and the NT* domain, following mutations of single asparagine residues to aspartic acid. Four different versions of fluorotryptophan were investigated, including 4-, 5-, 6-, and 7-fluorotryptophan, which were simultaneously installed by cell-free protein synthesis using 4-, 5-, 6-, and 7-fluoroindole as precursors for the tryptophan synthase present in the S30 extract. For comparison, the 1H chemical shifts of the corresponding nonfluorinated protein mutants produced with 13C-labeled tryptophan were also measured. The results show that the 19F chemical shifts respond more sensitively to the charge mutations than the 1H chemical shifts in the nonfluorinated references, but the chemical shift changes were much smaller than predicted by DFT calculations of fluoroindoles in the electric field of a partial charge in vacuum, indicating comprehensive dielectric shielding by water and protein. No straightforward correlation with the location of the charge mutation could be established.

The Resistive Cylindrical Chamber

A new generation of gaseous particle detectors named Resistive Cylindrical Chamber (RCC) (Cardarelli, 2021; Rocchi, 2022) [1,2] has been developed to overcome the limitations of Resistive Plate Chambers (Santonico and Cardarelli, 1981) [3] and broaden their application range. The principle behind this new technology consists in the transition from a planar to a cylindrical geometry while maintaining an almost planar electric field. The cylindrical structure of the electrodes allows to reach the following goals: increase the gas pressure to improve the intrinsic efficiency of the detector even for thin gas gaps or light gas mixtures; design the detector in order to produce an electric field gradient possibly useful to contain the development of the avalanche discharge. These features could lead to design detectors of simple mechanical realization with time resolution comparable with that of MRPCs maintaining a high efficiency of detection on a single thin gas-gap. The device pressurization could also allows to use new gases in view of the transition to eco-friendly gas.

Na<sup>+</sup> Mobility in PEO-Based Composite Solid-State Electrolytes by NMR

Charge transfer and mobility are essential for electrochemical processes in batteries, which need to be understood in detail for optimization, especially in the case of all-solid-state batteries. Wide line NMR is well-known in solid-state NMR and allows the quantification of ion mobility in ordered crystalline and amorphous structures. Temperature-dependent <sup>23</sup>Na-NMR is sensitive to ion mobility via longitudinal relaxation, but also via line analysis and transverse relaxation. As <sup>23</sup>Na is a spin 3/2 nucleus, <sup>23</sup>Na-NMR is also susceptible to electric field gradients caused by their nearest neighbor environment and, therefore, reflects not only the mobility of <sup>23</sup>Na<sup>+</sup> but also the molecular dynamics in the neighborhood, which are investigated in this paper. The named NMR methods were explored to study <sup>23</sup>Na<sup>+</sup> mobility in the solid electrolytes NaSICON (sodium (Na) Super Ionic CONductor, here Na<sub>3.4</sub>Zr<sub>2</sub>Si<sub>2.4</sub>P<sub>0.6</sub>O<sub>12</sub>), the salt NaTFSI (sodium bis(trifluoromethyl sulfonyl)imide), as well as in the polymer-based electrolytes PEO-NaSICON, PEO-NaTFSI, and PEO-NaTFSI-NaSICON.

Topology optimization of flexoelectric metamaterials with apparent piezoelectricity

The flexoelectric effect, coupling polarization and strain gradient as well as strain and electric field gradients, is universal to dielectrics, but, as compared to piezoelectricity, it is more difficult to harness as it requires field gradients and it is a small-scale effect. This drawback can be overcome by suitably designing multiscale metamaterials made of a non-piezoelectric base material but exhibiting apparent piezoelectricity. We develop a theoretical and computational framework to perform topology optimization of the representative volume element of such metamaterials by accurately modeling the governing equations of flexoelectricity using a Cartesian B-spline method, describing geometry with a level set, and resorting to genetic algorithms for optimization. We consider a multi-objective optimization problem where area fraction competes with each one of the four fundamental piezoelectric functionalities (stress/strain sensor/actuator). We computationally obtain Pareto fronts, and discuss the different geometries depending on the apparent piezoelectric coefficient being optimized. Our results show that optimal material architectures strongly depend on the specific functional property being optimized, and that, except for stress actuators, optimal structures are low-area-fraction lattices. In general, we find competitive estimations of apparent piezoelectricity as compared to reference materials such as quartz and PZT ceramics. This opens the possibility to design devices for sensing, actuation and energy harvesting from a much wider, cheaper and effective class of materials.

High dielectric filler for all-solid-state lithium metal battery

Lithium metal with its high theoretical capacity and low negative potential is considered one of the most important candidates to raise the energy density of all-solid-state batteries. However, lithium filament growth and its induced solid electrolyte decomposition pose severe challenges to realize a long cycle life. Here, dendrite growth in solid-state Li metal batteries is alleviated by introducing a high dielectric material, barium titanate, as a filler that removes the electric field gradients that catalyze dendrite formation. In symmetrical Li-metal cells, this results in a very small over-potential of only 48 mV at a relatively high current density of 1 mA cm−2, when cycling a capacity of 2 mA h cm−2 during 1700 h. The high dielectric filler improves the Coulombic efficiency and cycle life of full cells and suppresses electrolyte decomposition as indicated by solid-state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) measurements. This indicates that the high dielectric filler can suppress dendrite formation, thereby reducing solid electrolyte decomposition reactions, resulting in the observed low overpotentials and improved cycling efficiency.

Plausible photomolecular effect leading to water evaporation exceeding the thermal limit.

We report in this work several unexpected experimental observations on evaporation from hydrogels under visible light illumination. 1) Partially wetted hydrogels become absorbing in the visible spectral range, where the absorption by both the water and the hydrogel materials is negligible. 2) Illumination of hydrogel under solar or visible-spectrum light-emitting diode leads to evaporation rates exceeding the thermal evaporation limit, even in hydrogels without additional absorbers. 3) The evaporation rates are wavelength dependent, peaking at 520 nm. 4) Temperature of the vapor phase becomes cooler under light illumination and shows a flat region due to breaking-up of the clusters that saturates air. And 5) vapor phase transmission spectra under light show new features and peak shifts. We interpret these observations by introducing the hypothesis that photons in the visible spectrum can cleave water clusters off surfaces due to large electrical field gradients and quadrupole force on molecular clusters. We call the light-induced evaporation process the photomolecular effect. The photomolecular evaporation might be happening widely in nature, potentially impacting climate and plants' growth, and can be exploited for clean water and energy technologies.

Modeling the flexoelectric effect in semiconductors via a second-order collocation MFEM

In this paper, the flexoelectric effect in flexoelectric semiconductors (FSs) is studied via a second-order collocation mixed finite element method (MFEM) with the consideration of the strain gradient, electric field gradient, and drift-diffusion motion of carriers. In the present second-order collocation MFEM, the mechanical strain is assumed to be an independent quadratic polynomial function of local coordinates, and the kinematic constraint between the mechanical strain and displacement is approximately satisfied through a collocation method at 9 Gaussian quadrature points in each element. The setup for the electric field and electric potential also follows similar collocation strategy. Thus, except for the fundamental field variables, no additional DOFs are introduced. The accuracy of the proposed second-order collocation MFEM is verified by comparing numerical results with analytical solutions for a cantilever beam example. By performing the numerical experiments using the second-order collocation MFEM, the flexoelectric effect in FSs is simulated. Besides, we propose a novel mechanism for the converse flexoelectric effect in FSs which is induced by the diffusion motion of electrons. Numerical results indicate that by intensifying the diffusion motion of electrons, the converse flexoelectric effect, associated with the electric field gradient, could be enhanced.

Structure of the Local Environment and Hyperfine Interactions of <sup>57</sup>Fe Probe Nuclei in AMnO<sub>3</sub> (A = Sc, In)

The results of a Mössbauer study of hyperfine interactions of 57Fe probe nuclei in isostructural hexagonal manganites h-ScMnO3 and h-InMnO3 are presented. The results of measurements of the Mössbauer spectra at T TN, as well as calculations of the parameters of the electric field gradient tensor at 57Fe nuclei, demonstrated different behavior of the probe iron ions in these isostructural systems, reflecting the difference in the processes of defect formation in their crystal lattices. On the contrary, measurements at T TN did not reveal any differences in the local magnetic structure of 57Fe probe atoms in these oxides.

Exploring and optimizing the performance of inorganic Cs2TiBr6 halide perovskite solar cell with Cu2ZnSnS4 as hole transport layer by device simulation

To seek appropriate substitutes for lead-based perovskite, a perovskite solar cell (PSC) model using Cu2ZnSnS4 as the hole transport layer (HTL) and Cs2TiBr6 as the absorber layer is proposed in this study. The focus of this study is to discuss the drift and diffusion ability of charge carriers in the n-i-p structure formed by ZnO/Cs2TiBr6/Cu2ZnSnS4 under the action of the built-in electric field and concentration gradient. And based on the data simulated by SCAPS-1D, the effects of bandgap structure and device structure on carrier mobility, carrier lifetime, carrier diffusion length, improvement of device performance of the device were further explored. In addition, the effects of HTL types, thickness of HTL, absorber, and ETL, and defect density of absorber on device structure and behavior were analyzed through simulation by SCAPS-1D. The theoretical calculation results obtained by optimizing the structural parameters include 29.24% power conversion efficiency (PCE), 1.22 V open circuit voltage (V oc ), 26.79 mA cm−2 short circuit current (J sc ) and 89.78% fill factor (FF). The conclusion that the n-i-p structure formed by ZnO/Cs2TiBr6/Cu2ZnSnS4 is conducive to carrier migration is vindicated in this study, which enables devices to possess better performance. This study provides a theoretical basis for the application of Cu2ZnSnS4 in inorganic halide-based PSCs.

Temperature Dependence of Nuclear Quadrupole Resonance and the Observation of Metal-Ligand Covalency in Actinide Complexes: 35Cl in Cs2UO2Cl4.

We report a study of the temperature dependence of 35Cl nuclear quadrupole resonance (NQR) transition energies and spin-lattice relaxation times (T1) for 235U-depleted dicesium uranyl tetrachloride (Cs2UO2Cl4) aimed at elucidating electronic interactions between the uranium center and atoms in the equatorial plane of the UO22+ ion. The transition frequency decreases slowly with temperature below 75 K and with a more rapid linear dependence above this temperature. The spin-lattice relaxation time becomes shorter with temperature, and as temperatures increase, the T1 decrease becomes nearly quadratic. The observed trends are reproduced by a model that assumes phonon-induced fluctuations of the electric field gradient tensor and partial electron delocalization from Cl to U. The fit of the theoretical model to experimental data allows a Debye temperature of 96 K to be estimated. The generalization of this approach to investigations of covalency in actinide-ligand bonding is examined.