Symmetric Electron Research Articles

A theoretical study on symmetrical non-fullerene electron acceptors molecules on BDTPT based derivatives to enhance photovoltaic properties of organic solar cells

An innovative and promising approach to developing sustainable energy solutions and promoting an eco-friendly society is the use of organic solar cells. The key component for a solution-processed bulk-heterojunction organic solar cell is the photoactive layer’s embedded donor and acceptor components. This research presents seven modified molecules comprising the A–D–A type structural configuration, entitled A1–A7. All these designed moieties exhibit marvelous outcomes in optoelectronic features, including λmax and band gap, owing to non-fullerene acceptors in the terminal regions. All these compounds are computationally assessed by employing B3LYP at 6-31G (d,p) basis set using chloroform solvent. Compared to the reference molecule, the designed molecules (A1, A2, A4, A5, A6, A7) have reflected breakthrough results. The prerequisite for directing the practical application of designed acceptors is the efficient charge transfer, evidenced by coupling the J61 donor complex with the designed A5 acceptor.

Ensemble Generalization of the Perdew-Zunger Self-Interaction Correction: A Way Out of Multiple Minima and Symmetry Breaking.

The Perdew-Zunger (PZ) self-interaction correction (SIC) is an established tool to correct unphysical behavior in density functional approximations. Yet, the PZ-SIC is well-known to sometimes break molecular symmetries. An example of this is the benzene molecule, for which the PZ-SIC predicts a symmetry-broken electron density and molecular geometry, since the method does not describe the two possible Kekulé structures on an even footing, leading to local minima [Lehtola et al. J. Chem. Theory Comput. 2016, 12, 3195]. The PZ-SIC is often implemented with Fermi-Löwdin orbitals (FLOs), yielding the FLO-SIC method, which likewise has issues with symmetry breaking and local minima [Trepte et al. J. Chem. Phys. 2021, 155, 224109]. In this work, we propose a generalization of the PZ-SIC─the ensemble PZ-SIC (E-PZ-SIC) method─which shares the asymptotic computational scaling of the PZ-SIC (albeit with an additional prefactor). The E-PZ-SIC is straightforwardly applicable to various molecules, merely requiring one to average the self-interaction correction over all possible Kekulé structures, in line with chemical intuition. We showcase the implementation of the E-PZ-SIC with FLOs, as the resulting E-FLO-SIC method is easy to realize on top of an existing implementation of the FLO-SIC. We show that the E-FLO-SIC indeed eliminates symmetry breaking, reproducing a symmetric electron density and molecular geometry for benzene. The ensemble approach suggested herein could also be employed within approximate or locally scaled variants of the PZ-SIC and its FLO-SIC versions.

Fe based MOF encapsulating triethylenediamine cobalt complex to prepare a FeN3-CoN3 dual-atom catalyst for efficient ORR in Zn-air batteries

Single-atom catalysts show good oxygen reduction reaction (ORR) performance in metal-air battery. However, the symmetric electron distribution results in discontented adsorption energy of ORR intermediates and a lower ORR activity. Herein, Fe-Co dual-atom catalyst with FeN3-CoN3 configuration was prepared by encapsulating nitrogen-rich ion (triethylenediamine cobalt complex, [Co(en)3]3+) in Fe based MOF cage to greatly enhance ORR performance. Due to the confinement effect of the MOF cage, the encapsulated [Co(en)3]3+ is closer to Fe of MOF, thus easily generating FeN3-CoN3 sites. The FeN3-CoN3 sites can break the symmetric electron distribution of single-atom sites, optimizing adsorption energy of oxygen intermediate. Thus, FeCo-NC exhibits extraordinary ORR activity with a high half-wave potential of 0.915 V and 0.789 V in alkaline and acidic electrolyte, respectively, while it was 0.874 V and 0.79 V for Pt/C. The liquid and solid Zn-air batteries with FeCo-NC as cathode show higher peak power density and specific capacity. DFT results indicate that FeN3-CoN3 site can reduce the reaction energy barrier of the rate-determining step resulting in an excellent ORR performance.

A symmetric heterogate dopingless electron-hole bilayer TFET with ferroelectric and barrier layers

In this paper, a symmetric heterogate dopingless electron–hole bilayer tunnel field-effect transistor with a ferroelectric layer and a dielectric barrier layer (FBHD-EHBTFET) is proposed. FBHD-EHBTFET can not only avoid random doping fluctuation and high thermal budget caused by doping, but also solve the issue that conventional EHBTFETs are unable to use the self-alignment process during device manufacturing. The simultaneous introduction of the symmetric heterogate and dielectric barrier layer can significantly suppress off-state current (I off). Ferroelectric material embedded in the gate dielectric layer can enhance electron tunneling, contributing to improving on-state current (I on) and steepening average subthreshold swing (SS avg). By optimizing various parameters related to the gate, ferroelectric layer, and dielectric barrier layer, FBHD-EHBTFET can obtain the I off of 1.11 × 10–18 A μm−1, SS avg of 12.5 mV/dec, and I on of 2.59 × 10–5 A μm−1. Compared with other symmetric dopingless EHBTFETs, FBHD-EHBTFET can maintain high I on while reducing its I off by up to thirteen orders of magnitude and SS avg by at least 51.2%. Moreover, investigation demonstrates that both interface fixed charge and interface trap can increase I off, degrading the off-state performance of device. The study on FBHD-EHBTFET-based dynamic random access memory shows that it has the high read-to-current ratio of 1.1 × 106, high sense margin of 0.42 μA μm−1, and long retention time greater than 100 ms, demonstrating that it has great potential in low-power applications.

Cover Picture: Symmetric Electron Transfer Coordinates are Intrinsic to Bridged Systems: An ab Initio Treatment of the Creutz–Taube Ion (Angew. Chem. Int. Ed. 31/2024)

Cover Picture: Symmetric Electron Transfer Coordinates are Intrinsic to Bridged Systems: An ab Initio Treatment of the Creutz–Taube Ion (Angew. Chem. Int. Ed. 31/2024)

Titelbild: Symmetric Electron Transfer Coordinates are Intrinsic to Bridged Systems: An ab Initio Treatment of the Creutz–Taube Ion (Angew. Chem. 31/2024)

Titelbild: Symmetric Electron Transfer Coordinates are Intrinsic to Bridged Systems: An ab Initio Treatment of the Creutz–Taube Ion (Angew. Chem. 31/2024)

Symmetric Electron Transfer Coordinates are Intrinsic to Bridged Systems: An ab Initio Treatment of the Creutz-Taube Ion.

A long-standing question in electron transfer research concerns the number and identity of collective nuclear motions that drive electron transfer or localisation. It is well established that these nuclear motions are commonly gathered into a so-called electron transfer coordinate. In this theoretical study, we demonstrate that both anti-symmetric and symmetric vibrational motions are intrinsic to bridged systems, and that both are required to explain the characteristic shape of their intervalence charge transfer bands. Using the properties of a two-state Marcus-Hush model, we identify and quantify these two coordinates as linear combinations of normal modes from ab initio calculations. This quantification gives access to the potential coupling, reorganization energy and curvature of the potential energy surfaces involved in electron transfer, independent of any prior assumptions about the system of interest. We showcase these claims with the Creutz-Taube ion, a prototypical Class III mixed valence complex. We find that the symmetric dimension is responsible for the asymmetric band shape, and trace this back to the offset of the ground and excited state potentials in this dimension. The significance of the symmetric dimension originates from geometry dependent coupling, which in turn is a natural consequence of the well-established superexchange mechanism. The conceptual connection between the symmetric and anti-symmetric motions and the superexchange mechanism appears as a general result for bridged systems.

Symmetric Electron Transfer Coordinates are Intrinsic to Bridged Systems: An ab Initio Treatment of the Creutz–Taube Ion

AbstractA long‐standing question in electron transfer research concerns the number and identity of collective nuclear motions that drive electron transfer or localisation. It is well established that these nuclear motions are commonly gathered into a so‐called electron transfer coordinate. In this theoretical study, we demonstrate that both anti‐symmetric and symmetric vibrational motions are intrinsic to bridged systems, and that both are required to explain the characteristic shape of their intervalence charge transfer bands. Using the properties of a two‐state Marcus–Hush model, we identify and quantify these two coordinates as linear combinations of normal modes from ab initio calculations. This quantification gives access to the potential coupling, reorganization energy and curvature of the potential energy surfaces involved in electron transfer, independent of any prior assumptions about the system of interest. We showcase these claims with the Creutz–Taube ion, a prototypical Class III mixed valence complex. We find that the symmetric dimension is responsible for the asymmetric band shape, and trace this back to the offset of the ground and excited state potentials in this dimension. The significance of the symmetric dimension originates from geometry dependent coupling, which in turn is a natural consequence of the well‐established superexchange mechanism. The conceptual connection between the symmetric and anti‐symmetric motions and the superexchange mechanism appears as a general result for bridged systems.

Effect of Zn2+ doping on the structure and metal–insulator transition of La2CuO4 ceramics

The structure and electrical properties of layered perovskites La2Cu1-xZnxO4 have been investigated. The resistivity of these samples has been measured in the temperature range of 90–300 K. The Zn2+doping induces a shift of the metal–insulator transition temperature towards the high-temperature region. The d9 electronic configuration of Cu2+ in La2CuO4 leads to an uneven distribution of electron clouds, inducing axial stretching of the surrounding oxygen octahedra and resulting in Jahn-Teller distortion. After Zn2+ doping, the charge compensation induces a partial transformation of Cu2+ to Cu+. As a result, the positions occupied by Cu2+ are replaced by Zn2+ and Cu+ with perfectly symmetric electron clouds in the 3d10 outer electronic configuration, thus suppressing the Jahn-Teller effect. This shifts the phonon scattering, which is responsible for the emergence of the metal’s conductive properties, to higher temperatures.

Fe-N co-doped carbon nanofibers with Fe3C decoration for water activation induced oxygen reduction reaction

ABSTRACT Proton activity at the electrified interface is central to the kinetics of proton-coupled electron transfer (PCET) reactions in electrocatalytic oxygen reduction reaction (ORR). Here, we construct an efficient Fe3C water activation site in Fe-N co-doped carbon nanofibers (Fe3C-Fe1/CNT) using an electrospinning-pyrolysis-etching strategy to improve interfacial hydrogen bonding interactions with oxygen intermediates during ORR. In situ Fourier transform infrared spectroscopy and density functional theory studies identified delocalized electrons as key to water activation kinetics. Specifically, the strong electronic perturbation of the Fe–N4 sites by Fe3C disrupts the symmetric electron density distribution, allowing more free electrons to activate the dissociation of interfacial water, thereby promoting hydrogen bond formation. This process ultimately controls the PCET kinetics for enhanced ORR. The Fe3C-Fe1/CNT catalyst demonstrates a half-wave potential of 0.83 V in acidic media and 0.91 V in alkaline media, along with strong performance in H2-O2 fuel cells and Al-air batteries.

Properties of collisional plasma sheath with ionization source term and two-temperature electrons in an oblique magnetic field

A collisional magnetized plasma sheath with two groups of electrons has been studied using a fluid model including the effects of the ionization source term and the collisional force between ions and neutral atoms. Two kinds of non-Maxwellian descriptions of electron velocity distribution, non-extensive distribution and truncated distribution, are applied in the model, and the ionization effects of both kinds are considered. By applying Sagdeev potential, the modified Bohm sheath criterion is derived. The effects of ionization, magnetic field, and high-temperature electron concentration ratio on plasma sheath density, potential, sheath thickness, and ion kinetic energy are studied. In cases with high background gas density, ion density accumulates at the sheath edge position, forming a peak and manifesting as a rapid drop in the potential profile. The distribution characteristics of electrons have a significant impact on the transport properties of ions. Oscillations and non-monotonic characteristics of net charge near the sheath edge occur as the magnetic field angle increases, leading to an increase in the sheath layer width. It can be seen that in the case of a collisional sheath structure with high-temperature electrons, it is essential to consider the sheath changes induced by the ionization and the collisional force. Compared to a symmetric electron velocity distribution, the actual thickness of the sheath layer in a truncated electron distribution assumption could be significantly reduced.

A new approach for fast field calculation in electrostatic electron lens design and optimization

In electron optics, calculation of the electric field plays a major role in all computations and simulations. Accurate field calculation methods such as the finite element method (FEM), boundary element method and finite difference method, have been used for years. However, such methods are computationally very expensive and make the computer simulation challenging or even infeasible when trying to apply automated design of electrostatic lens systems with many free parameters. Hence, for years, electron optics scientists have been searching for a fast and accurate method of field calculation to tackle the aforementioned problem in the design and optimization of electrostatic electron lens systems. This paper presents a novel method for fast electric field calculation in electrostatic electron lens systems with reasonably high accuracy to enable the electron-optical designers to design and optimize an electrostatic lens system with many free parameters in a reasonably short time. The essence of the method is to express the off-axis potential in an axially symmetrical coordinate system in terms of derivatives of the axial potential up to the fourth order, and equate this to the potential of the electrode at that axial position. Doing this for a limited number of axial positions, we get a set of equations that can be solved to obtain the axial potential, necessary for calculating the lens properties. We name this method the fourth-order electrode method because we take the axial derivatives up to the fourth order. To solve the equations, a quintic spline approximation of the axial potential is calculated by solving three sets of linear equations simultaneously. The sets of equations are extracted from the Laplace equation and the fundamental equations that describe a quintic spline. The accuracy and speed of this method is compared with other field calculation methods, such as the FEM and second order electrode method (SOEM). The new field calculation method is implemented in design/optimization of electrostatic lens systems by using a genetic algorithm based optimization program for electrostatic lens systems developed by the authors. The effectiveness of this new field calculation method in optimizing optical parameters of electrostatic lens systems is compared with FEM and SOEM and the results are presented. It should be noted that the formulation is derived for general axis symmetrical electrostatic electron lens systems, however the examples shown in this paper are with cylindrical electrodes due to the simplicity of the implementation in the software.

In situ modulating coordination fields of single-atom cobalt catalyst for enhanced oxygen reduction reaction

Single-atom catalysts, especially those with metal−N4 moieties, hold great promise for facilitating the oxygen reduction reaction. However, the symmetrical distribution of electrons within the metal−N4 moiety results in unsatisfactory adsorption strength of intermediates, thereby limiting their performance improvements. Herein, we present atomically coordination-regulated Co single-atom catalysts that comprise a symmetry-broken Cl−Co−N4 moiety, which serves to break the symmetrical electron distribution. In situ characterizations reveal the dynamic evolution of the symmetry-broken Cl−Co−N4 moiety into a coordination-reduced Cl−Co−N2 structure, effectively optimizing the 3d electron filling of Co sites toward a reduced d-band electron occupancy (d5.8 → d5.28) under reaction conditions for a fast four-electron oxygen reduction reaction process. As a result, the coordination-regulated Co single-atom catalysts deliver a large half-potential of 0.93 V and a mass activity of 5480 A gmetal−1. Importantly, a Zn-air battery using the coordination-regulated Co single-atom catalysts as the cathode also exhibits a large power density and excellent stability.

Recent advances in Fe‐N‐C single‐atom site coupled synergistic catalysts for boosting oxygen reduction reaction

AbstractMetal–air batteries, fuel cells, and electrochemical H2O2 production currently attract substantial consideration in the energy sector owing to their efficiency and eco‐consciousness. However, their broader use is hindered by the complex oxygen reduction reaction (ORR) that occurs at cathodes and involves intricate electron transfers. Despite the significant ORR performance of platinum‐based catalysts, their high cost, operational limitations, and susceptibility to methanol poisoning hinder broader implementation. This emphasizes the need for efficient non‐precious metal‐based ORR electrocatalysts. A promising approach involves utilizing single‐atom catalysts (SACs) featuring metal–nitrogen–carbon (M‐N‐C) coordination sites. SACs offer advantages such as optimal utilization of metal atoms, uniform active centers, precisely defined catalytic sites, and robust metal–support interactions. However, the symmetrical electron distribution around the central metal atom of a single‐atom site (M‐N4) often results in suboptimal ORR performance. This challenge can be addressed by carefully tailoring the surrounding environment of the active center. This review specifically focuses on recent advancements in the Fe‐N4 environment within Fe‐N‐C SACs. It highlights the promising strategy of coupling Fe‐N4 sites with metal clusters and/or nanoparticles, which enhances intrinsic activity. By capitalizing on the interplay between Fe‐N4 sites and associated species, overall ORR performance improved. The review combines findings from experimental studies and density functional theory simulations, covering synthesis strategies for Fe‐N‐C coupled synergistic catalysts, characterization techniques, and the influence of associated particles on ORR activity. By offering a comprehensive outlook, the review aims to encourage research into high‐efficiency Fe single‐atom sites coupled synergistic catalysts for real‐world applications in the coming years.

2D surfaces twisted to enhance electron freedom toward efficient advanced oxidation processes

Two-dimensional (2D)-interface engineering for designing effective electron-rich catalyst center is pivotal in manipulating the catalytic behaviors and activity, but still challenging. Here, we’ve successfully twisted the surfaces of the 2D layered FeOCl, fulfilling the targeted fine-tuning of its Fe sites. The obtained new catalyst can boost peroxymonosulfate activation for reactive species with much lower energy barriers and efficiently oxidized target organic with almost 41 orders of magnitude faster reaction kinetics than pristine FeOCl. The increased degree of freedom of electron around Fe site has been identified as the key driver. The distorted geometry structure around Fe has led to an increased polarization of charge distribution, associating with less symmetric electron valence cloud and higher electron mobility. Thus, the twisted surfaces enable a much enhanced interfacial charge transfer between Fe site and the electron-deficient peroxymonosulfate. This work highlights the concept of twisted surface construction toward efficient advanced oxidation catalyst design.

Drain current sensitivity analysis using a surface potential-based analytical model for AlGaN/GaN double gate MOS-HEMT

In this research, a surface potential-based drain current model for an AlGaN/GaN symmetrical double-gate metal oxide semiconductor high electron mobility transistor (DG-MOSHEMT) is proposed and used to detect label-free biomolecules for the first time. The model is applied for a nanocavity-based DG-MOSHEMT and works on the concept of dielectric modulation to detect biomolecules like uricase, urease, streptavidin, protein, biotin, ChOx, and APTES(3-aminopropyltriethoxysilane). The performance indicators, such as a change in drain ON current (ΔION), drain current sensitivity (SION), transconductance sensitivity (Sgm), and output conductance sensitivity (Δgd), are used to assess the device's efficacy. Numerical simulations are conducted to verify the model's accuracy and quantify its sensitivity. The DG-MOSHEMT device elicited exceptional sensitivity towards the uricase biomolecule, surpassing all other analytes tested, with SION = 0.328, Sgm = 0.197, and Δgd = 28.1 mS/mm. Furthermore, the model considers the contribution of the first two sub-bands of the quantum well and competently captures the fluctuation in drain ON current and sensitivity. A comprehensive sensitivity analysis of the drain current is conducted by altering physical parameters such as cavity length, thickness, gate length and barrier layer thickness. Notably, the sensitivity SION is significantly improved with cavity length and thickness for the optimized AlGaN barrier layer.

Designing Sulfate Crystals with Strong Optical Anisotropy through π‐Conjugated Tailoring

AbstractSulfate crystals typically exhibit minimal optical anisotropy due to the near‐zero polarizability anisotropy (δ) of [SO4]2− tetrahedra, arising from highly symmetrical electron clouds. Recent research sought to enhance δ via chemical modifications, such as fluorination. However, the resultant crystals often maintain subpar optical anisotropy, frequently with birefringence values below 0.1. In this study, we have uncovered that δ can be significantly strengthened by chemically tailoring the tetrahedral [SO4]2− with anisotropic π‐conjugated modules. This has been demonstrated by several newly proposed S−O‐Org (Org: π‐conjugated organic species) moieties, which show a sharp increase in δ based on theoretical computations. To further validate this experimentally, we synthesized and characterized six new 3‐pyridinesulfonate crystals with the formula A(3‐C5H4NSO3) ⋅ xH2O (A=Li, Ag, K, Rb, Cs, and NH4; x=0 and 1). Notably, these materials exhibit strong optical anisotropy, with birefringence values ranging from 0.240 to 0.312 at 546 nm. These values are approximately 23 to 145.5 times greater than those of corresponding sulfates, and they outperform a vast number of sulfate‐related optical materials, thus verifying the effectiveness of the proposed strategy. Furthermore, the title compounds exhibit diverse microstructure peculiarities influenced by the size and binding natures of the counter cations.

Designing Sulfate Crystals with Strong Optical Anisotropy through π-Conjugated Tailoring.

Sulfate crystals typically exhibit minimal optical anisotropy due to the near-zero polarizability anisotropy (δ) of [SO4 ]2- tetrahedra, arising from highly symmetrical electron clouds. Recent research sought to enhance δ via chemical modifications, such as fluorination. However, the resultant crystals often maintain subpar optical anisotropy, frequently with birefringence values below 0.1. In this study, we have uncovered that δ can be significantly strengthened by chemically tailoring the tetrahedral [SO4 ]2- with anisotropic π-conjugated modules. This has been demonstrated by several newly proposed S-O-Org (Org: π-conjugated organic species) moieties, which show a sharp increase in δ based on theoretical computations. To further validate this experimentally, we synthesized and characterized six new 3-pyridinesulfonate crystals with the formula A(3-C5 H4 NSO3 ) ⋅ xH2 O (A=Li, Ag, K, Rb, Cs, and NH4 ; x=0 and 1). Notably, these materials exhibit strong optical anisotropy, with birefringence values ranging from 0.240 to 0.312 at 546 nm. These values are approximately 23 to 145.5 times greater than those of corresponding sulfates, and they outperform a vast number of sulfate-related optical materials, thus verifying the effectiveness of the proposed strategy. Furthermore, the title compounds exhibit diverse microstructure peculiarities influenced by the size and binding natures of the counter cations.

Relativistic resolution-of-the-identity with Cholesky integral decomposition.

In this study, we present an efficient integral decomposition approach called the restricted-kinetic-balance resolution-of-the-identity (RKB-RI) algorithm, which utilizes a tunable RI method based on the Cholesky integral decomposition for in-core relativistic quantum chemistry calculations. The RKB-RI algorithm incorporates the restricted-kinetic-balance condition and offers a versatile framework for accurate computations. Notably, the Cholesky integral decomposition is employed not only to approximate symmetric large-component electron repulsion integrals but also those involving small-component basis functions. In addition to comprehensive error analysis, we investigate crucial conditions, such as the kinetic balance condition and variational stability, which underlie the applicability of Dirac relativistic electronic structure theory. We compare the computational cost of the RKB-RI approach with the full in-core method to assess its efficiency. To evaluate the accuracy and reliability of the RKB-RI method proposed in this work, we employ actinyl oxides as benchmark systems, leveraging their properties for validation purposes. This investigation provides valuable insights into the capabilities and performance of the RKB-RI algorithm and establishes its potential as a powerful tool in the field of relativistic quantum chemistry.

Dose symmetric electron diffraction tomography (DS-EDT): Implementation of a dose-symmetric tomography scheme in 3D electron diffraction

Beam sensitive nanomaterials such as zeolites or metal-organic frameworks (MOF) represent a great challenge for crystallographic structure determination and refinement. The strong electron-matter interaction and the high spatial resolution achievable make electron diffraction the technique of choice for particles of sizes below a micrometer and many different 3-dimensional electron diffraction (3D ED) techniques have been developed in recent years. Nevertheless, beam sensitivity of the samples can lead to the crystal structure being damaged during the data acquisition impeding the determination of its structure. A simple way to reduce beam damage is to lower the dose during the experiment. However, this implies weaker diffraction intensities which can become problematic for the exploitation of the data.In order to obtain complete data sets with strong intensities without damaging the crystals, we developed the dose symmetric electron diffraction tomography (DS-EDT) method, combining the low-dose electron diffraction tomography (LD-EDT) technique with the dose-symmetric tomography scheme known from cryo-EM. In order to reduce the dose on an individual crystal and still obtain enough data for a structure solution and refinement, we partition the dose over several crystals. The individual datasets are then merged in order to achieve the necessary completeness. On two test structures we first show that merging of data from small domains of the reciprocal space is indeed sufficient to obtain reliable data for structure solution and refinement. Second, we show on the beam sensitive manganese formate that high-quality data can be obtained on a few frames while the frames that have suffered from beam damage can still be used to determine the orientation matrix and the unit cell of the crystals. The results from the dynamical refinement on the obtained data show a high accuracy of the atom positions. In this way, DS-EDT can reduce the total dose on an individual crystal by an order of magnitude with respect to the already very dose-efficient LD-EDT.