Electron Localization Research Articles

Controlling the Polarity of Metal-Organic Frameworks to Promote Electrochemical CO2 Reduction.

The addition of polar functional groups to porous structures is an effective strategy for increasing the ability of metal-organic frameworks (MOFs) to capture CO2 by enhancing interactions between the dipoles of the polar functional groups and the quadrupoles of CO2. However, the potential of MOFs grafted to polar functional group to activate CO2 has not been investigated in the context of CO2 electrolysis. In this study, we report a mixed-ligand strategy to incorporate various functional groups in the MOFs. We found that substituents with strong polarity led to increased catalytic performance of electrochemical CO2 reduction for these polarized MOFs. Both experimental and theoretical evidence indicates that the presence of polar functional groups induces a charge redistribution in the micropores of MOFs. We have shown that higher electron densities of sp2-carbon atoms in benzimidazolate ligands reduces the energy barrier to generate *COOH, which is simultaneously controlled by the mass transfer of CO2. Our research offers an effective method of disrupting local electron neutrality in the pores of electrocatalysts/supports to activate CO2 under electrochemical conditions.

On-Surface Atomic Scale Qubit Platform.

Recent advances in scanning probe microscopy combined with electron spin resonance have revealed that localized electron spins on or near surfaces can be utilized as building blocks for the bottom-up assembly of functional quantum-coherent nanostructures. In this perspective, we review the recent advances, lay out advantages of this platform and outline the challenges that lie ahead on the way to the application of on-surface atomic spins to quantum information science and quantum computing.

Mechanochemical Synthesis, Characterization and Reactivity of a Room Temperature Stable Calcium Electride.

A new calcium-based Room temperature Stable Electride (RoSE), K[{Ca[N(Mes)(SiMe3)]3(e-)}2K3] (2), is successfully synthesized from the reaction of a calcium tris-amide, [Ca{N(Mes)(SiMe3)}3K] (1) (Mes = 2,4,6-trimethylphenyl), with potassium under mechanochemical treatment. The dimeric structure of K[{Ca[N(Mes)(SiMe3)]3(e-)}2K3] is calculated using ab initio random structure searching (AIRSS) methods. This shows the existence of highly localized anionic electrons (e-) and suggests poor electrical conductance, as confirmed via electroconductivity measurements. The two anionic electrons in 2 are strongly antiferromagnetically coupled, thus in agreement with the largely diamagnetic response from magnetometry. Reaction of 2 with pyridine affords 4,4'-bipyridine, while reaction with benzene gives C-H activation and formation of a calcium hydride complex, [K(η6-C6H6)4][{Ca[N(Mes)(SiMe3)](H)}2K3] (3). Computational DFT analysis reveals the crucial role played by the ligand framework in the stabilization of this new Ca-hydride complex.

Mechanisms of enhanced performance in Zr4+/Ta5+ codoped rutile-TiO2 ceramics via broadband dielectric spectroscopy.

Aliovalent dopant codoped rutile-TiO2 materials have garnered attention due to their excellent performance properties, characterized by low loss tangent (tanδ), high dielectric permittivity (ε'), and stable ε' over a broad temperature range. This performance is primarily due to the electron-pinned defect-dipoles (EPDDs) of the complex defects [Formula: see text]Ti3+-[Formula: see text]Ti3+BTi. Notably, the excellent dielectric properties in ZrxTa2.5%Ti0.975-xO2 (Zr-TTO) ceramics can be achieved using the traditional mixed oxide method without the EPDDs, due to the absence of A3+ (acceptor doping ions). Instead, the existence of localized free electrons and oxygen vacancies ([Formula: see text]) in Zr-TTO structures, due to doping ions and the sintering process, was confirmed by X-ray photoelectron and Raman spectroscopies. These ceramics exhibited ε'~ 2 × 104 and tanδ < 0.03 at 1kHz and 25°C in the 2.5-10%Zr-TTO samples. Moreover, all ceramics demonstrated a maximum ε' change (∆ε') of less than ±15% over the temperature range suitable for X7R and X8R type ceramic capacitors. Significantly, the change in ε' related to relative humility was calculated to be less than ±0.5% over the range of 50-95% RH, indicating the environmental stability of the dielectric properties, which is essential for capacitor applications. Investigations suggested that at least four mechanisms contributed to this system: the intrinsic effect of ionic polarization, Ti4+ · e- -[Formula: see text]- Ti4+ · e- and Ti4+ · e- - [Formula: see text] defects, interfacial polarization at insulating grain boundaries, and non-Ohmic contact between the surface sample and the metal electrode.

Atomic-Scale Mechanism of Enhanced Electron-Phonon Coupling at the Interface of MgB2 Thin Films.

In conventional Bardeen-Cooper-Schrieffer (BCS) superconductors, electron-phonon coupling is the fundamental mechanism of superconductivity. For instance, the superconductivity of magnesium diboride (MgB2) comes from the coupling between E2g modes (in-plane boron-boron bond vibrations) and self-doped charge carriers. In thin films and ceramics of BCS superconductors, interfaces with discontinuous chemical bonds may alter the local electron-phonon coupling. However, such effects remain largely unexplored. Here, we investigate the heterointerface of the MgB2 film on the SiC substrate at the atomic scale using electron microscopy and spectroscopy. We detect the presence of a thin MgO layer with a thickness of ∼1 nm between MgB2 and SiC. Atomic-level electron energy loss spectra (EELS) show MgB2-E2g mode splitting and softening near the MgB2/MgO interface, which enhances electron-phonon coupling at the interface. Our findings highlight the potential of interface engineering to enhance superconductivity via modulating local phonon states and/or electron states.

Prediction of stable structure and unique charge transfer in Li–Pt intermetallic compounds under pressure

The exploration of new intermetallic compounds is of great significance for basic research and practical application. There is a huge electronegativity difference between Li and Pt, and the metals exhibit interesting and diverse properties; however, the structural behavior of Li–Pt intermetallics with different ratios under high pressure has not been systematically studied. In this study, an intelligent structure search method based on a particle swarm optimization algorithm combined with first-principles calculations was used to extensively explore the stable structures and unique conditions governing charge transfer in Li–Pt intermetallic compounds under different pressures. In addition to reproducing the known LiPt (P6‾m2) and Li2Pt (P6/mmm), the simulation was consistent with the experimental results. New phases were also found by calculation: LiPt3(Cmmm), Li2Pt (P3‾m1), and Li4Pt (I4/m) at ambient pressure; Li3Pt (Fm3‾m), Li4Pt (R3‾m), and Li5Pt (P6/mmm) at 10 GPa; and Li5Pt (P3‾m1) at 20 GPa. Bader charge analysis and electron localization function (ELF) mapping showed that the transition metal (Pt) atoms exhibit unusual oxidation states both under ambient and high pressure, and more electrons were localized on Pt as the Li content increased. The highest negative valence state was approximately −4. Intermetallic compounds LiPt3 (Cmmm) and Li2Pt (P6/mmm) were prepared successfully by arc melting furnace. The reliability of structure prediction method and pseudo potential selection was verified. This work demonstrates that tuning the pressure and stoichiometry is an effective means of forming novel, stable intermetallic compounds.

Crystal Growth, Structural Elucidation, Chemical Reactivity, Topology Exploration (ELF, LOL, AIM, RDG) and NLO Activity of 4-Cumyl Phenol Crystal Using Quantum Chemical Calculation

The main objective of the study is to analyze the structural behavior and NLO activity of 4-cumyl phenol by experimental and theoretical spectroscopic techniques. Its computational result is compared with the cumene compound. The optimized structural parameters of the title compound were computationally obtained at the B3LYP/6-31G (d, p) basis set. The fundamental modes of vibration were examined by experimental FT-IR, and FT-Raman techniques. The distribution of the vibrational bands was carried out with the help of normal coordinate analysis (NCA). The resulting harmonic wavenumbers were scaled by using NCA method. Topological analysis, such as Electron localization function (ELF), natural bond orbital analysis (NBO), reduced density gradient (RDG) and atoms in molecule (AIM) analysis, molecular electrostatic potential (MEP) have been used to evaluate the intermolecular interaction, especially the hydrogen bonds. UV-visible spectrum of the compound was recorded in the region 200–900 nm and the electronic properties and HOMO-LUMO energies were calculated by time dependent density functional theory approach.

Vanadate-Mediated Mismatch Configuration over the Reconstructed Nickel-Iron Electrocatalyst for Boosting Alkaline Oxygen Evolution.

During the oxygen evolution reaction (OER), catalyst candidates that can fully trigger self-reconstruction to derive active species with favorable configurations are expected to overcome the sluggish reaction kinetics. Herein, we innovatively propose the introduction of heterogeneous vanadate dopants into nickel-iron alloy precatalysts, where the crystal mismatch structure induces local electron delocalization in the hexagonal close packed alloy phase, thereby facilitating adequate electrochemical reconstruction to form (oxy)hydroxides as the real catalytic species. Simultaneously, the participation of vanadate in the reconstruction also triggers mismatch in the derived (oxy)hydroxides, reinforcing the metal-oxygen covalence, so that lattice oxygen activation is kinetically favorable and facilitates the OER via the lattice oxygen pathway. Optimized reconstructed catalyst r-NiFeVOx-NF exhibits a low overpotential of 220 mV at current densities of 10 mA cm-2 and considerably stable operation. Our study opens up opportunities for achieving robust OER performance through the design and fabrication of the mismatch catalytic configuration.

Exploring chemical reactivity through a combined conceptual DFT and ELF topology approach.

In a proof-of-concept study, we explore how a combined approach using the topology of the electron localization function (ELF) and the condensed dual descriptor (DD) function can guide the optimal orientation between reactants and mimic the potential energy surfaces of molecular systems at the beginning of the chemical pathway. The DD has been chosen for its ability to evaluate the regioselectivity of neutral and soft species and to potentially mimic the interaction energy obtained from the mutual interactions between nucleophilic and electrophilic regions of the building blocks under perturbative theory. Our method has been illustrated with examples in which the optimal orientation of several systems can be successfully identified. The limitations of the presented model in predicting chemical reactivity are outlined in particular the influence of the selected condensation scheme.

Lattice defects and surface adsorption properties of gold-bearing chalcopyrite: A theoretical study based on DFT

Chalcopyrite (CuFeS2), as one of the carrier minerals of gold, undergoes significant alterations in lattice and surface properties upon doping with gold impurities. These changes markedly influence its separation and purification techniques, especially flotation. Using Density Functional Theory (DFT) based on first-principles, we analyze the influence of gold impurities on the lattice defects and surface properties of chalcopyrite. We developed an adsorption model using prop-2-yn-1-yl diethylcarbamodithioate (PDEC), a sulfur ester collector with an ethynyl group, on gold-infused chalcopyrite to elucidate the adsorption mechanism. Our findings indicate that the Au atom primarily occupies interstitial sites within the chalcopyrite lattice, resulting in an expanded lattice structure. Despite the doping, the lattice remains a p-type semiconductor with increased conductivity, facilitated by Au 6 s orbitals contributing to impurity levels within the conduction band from 2 to 4 eV. Additionally, there is a marked rise in spin-up electrons, with Integrated |Spin Density| results showing greater electron localization in Cu15Fe16S32Au and Cu16Fe16S32Au compared to ideal chalcopyrite crystal (Cu16Fe16S32). The Au atom exhibits maximum stability when adsorbed onto the S-Fe bonds on chalcopyrite surfaces, primarily forming covalent bonds through electron acceptance from Fe 3d orbitals. The presence of gold impurities decreases the collector's adsorption energy on the chalcopyrite (112) surface. However, PDEC exhibits enhanced adsorption performance relative to Al-DECDT and Z-200, primarily due to the chelation between thiocarbonyl and ethynyl groups of PDEC and the gold-bearing chalcopyrite (112) surface. Electron donation from Fe 4p orbitals of surface to the S 3 s and 3p orbitals of collector forms a sigma bond, while the ethynyl group undergoes hybridization with the Au 5d orbitals from −5 to −2.5 eV, fostering stable electron transfer.

Prediction of comprehensive properties and their hydrogen performance of Mg2XH6(X=Mn, Fe, Co, Ni) perovskite hydrides based on first principles

Hydrogen storage materials are very critical for hydrogen energy utilization. Cubic Mg2XH6(X = Mn, Fe, Co, Ni) hydrogen storage materials are investigated by first principles calculation. The structural stability are confirmed by complex consideration of phonon spectrum, formation energies and elastic constants. They are brittle and hard materials with high temperature applicable potential. Mg2MnH6 and Mg2CoH6 are magnetic compounds while Mg2FeH6 and Mg2NiH6 are non-magnetic materials. Mg2MnH6 and Mg2FeH6 are semiconductors with bandgap of 1.867 eV and 3.318 eV, respectively, indicating they are applicable in optoelectronic field, while Mg2CoH6 and Mg2NiH6 are metallic in energy band structure. They are all ionic compounds which are confirmed by Cauchy pressure, electronic density difference and electronic localization function. Their hydrogen storage capacity are all over 5.2 wt%, which are favorable in practical use. And the moderate desorption temperature of 328.9 K of Mg2MnH6 suggests it is a promising candidate for hydrogen storage.

Exploring the adsorption characteristics of quinoline derivatives on iron via ab initio DFT simulations and COSMO-RS profiles

Quinoline derivatives have been the subject of extensive research due to their excellent electronic properties and wide range of applications. This study conducts a comprehensive computational examination of the adsorption properties of substituted quinoline derivatives on Fe(110) surfaces. Four specific compounds, namely 2-amino-7-hydroxy-4-phenyl-1,4-dihydroquinoline-3-carbonitrile (QN1), 2-amino-7-hydroxy-4-(p-tolyl)-1,4-dihydroquinoline-3-carbonitrile (QN2), 2-amino-7-hydroxy-4-(4-methoxyphenyl)-1,4-dihydroquinoline-3-carbonitrile (QN3), and 2-amino-4-(4-(dimethylamino)phenyl)-7-hydroxy-1,4-dihydroquinoline-3-carbonitrile (QN4) were investigated using first-principles density functional theory (DFT) calculations along with COSMO-RS analysis for solvation properties. Our results revealed that the presence of functional groups significantly influence the adsorption strength on Fe(110) surfaces. Quinoline molecules have adsorbed on the iron surface through complex mechanisms involving physical interactions and charge transfer. Specifically, QN1 and QN4 showed strong physical interactions with iron atoms while QN2 and QN3 exhibited high affinity to coordinate with Fe atoms. The stability of coordinated quinolines was enhanced by a notable charge redistribution and bond formation as observed via projected density of states (PDOS). On the other hand, electron density difference (EDD) and electron localization function (ELF) iso-surfaces highlighted the critical role of van der Waals interactions, predominantly influenced by nitrogen atoms, in stabilizing the adsorbed molecules. The COSMO-RS analysis elucidated the solvation characteristics, emphasizing the importance of hydrogen bond donor (HBD) and hydrogen bond acceptor (HBA) in the interaction of quinolines with water molecules. Overall, this study provides crucial insights into the molecular mechanisms underlying the corrosion inhibition properties of quinoline derivatives, emphasizing the influence of functional groups and solvation effects on adsorption behavior and stability.

Disclosing the magnetic ground state of PrBaMn2O6

In this work, we report a neutron diffraction study on a single crystal of the layered PrBaMn2O6 perovskite. This compound undergoes two consecutive magnetic transitions with decreasing temperature. At TC ≈ 309 K, a long-range ferromagnetic ordering is established with the Mn magnetic moments oriented along the c axis. Below TN ≈ 240 K, a spin reorientation gives rise to a sudden decrease of the magnetization and the formation of an antiferromagnetic order. This magnetic transition is also accompanied by an electronic localization caused by a structural phase transition from a high-temperature tetragonal phase (P4/mmm) into a low-temperature orthorhombic one (P21am). Our neutron diffraction study at 12 K has unambiguously identified that the ground magnetic structure for this compound is a layered antiferromagnetic structure along the c axis with the Mn moments oriented in the ab plane along one diagonal of the primitive tetragonal cell. No sign of magnetic scattering associated to a CE-type magnetic structure was found in our study, discarding its occurrence in this compound. This result excludes the occurrence of a charge order transition to account for the electronic localization and it is fully consistent with previous structural studies showing a unique crystallographic site for Mn atom in the low-temperature phase. A symmetry analysis was carried out to identify the magnetic space group of the ferromagnetic order above TN and the two possible groups for the antiferromagnetic ordering below TN.

In Situ-Constructed Multifunctional Composite Anode with Ultralong-Life Toward Advanced Lithium-Metal Batteries.

Metallic lithium is the most competitive anode material for next-generation high-energy batteries. Nevertheless, the extensive volume expansion and uncontrolled Li dendrite growth of lithium metal not only cause potential safety hazards but also lead to low Coulombic efficiency and inferior cycling lifespan for Li metal batteries. Herein, a multifunctional dendrite-free composite anode (Li/SnS2) is proposed through an in situ melt-infusion strategy. In this configuration, the 3D cross-linked porous Li2S/Li22Sn5 framework facilitates the rapid penetration of electrolytes and accommodates the volume expansion during the repeated Li-plating process. Meanwhile, the lithiophilic Li2S phases with a low Li+ transport barrier ensure preferential Li deposition, effectively avoiding uneven electron distribution. Moreover, the Li22Sn5 electron conductors with appropriate Li+ bonding ability guarantee rapid charge transport and mass transfer. Most importantly, the steady multifunctional skeleton with sufficient inner interfaces (Li2S/Li22Sn5) in the whole electrode, not only realizes the redistribution of the localized free electron, contributing to the decomposition of Li clusters, but also induces a planar deposition model, thus restraining the generation of Li dendrites. Consequently, an unprecedented cyclability of over 6500h under an ultrahigh areal capacity of 10mAhcm-2 and a current rate of 20mAcm-2 is achieved for the prepared Li2S/Li22Sn5 composite anode. Moreover, the assembled Li/SnS2||LiFePO4 (LFP) pouch full-cells also demonstrate remarkable rate capability and a convincing cycling lifespan of more than 2000 cycles at 2 C.

Probing electron localization and delocalization in the selective long-range tight-binding model

Probing electron localization and delocalization in the selective long-range tight-binding model

Theoretical insights of 2D Fe3GeTe2/In2Se3 multiferroic vdW heterostructure based gas sensors for high-performance NO detecting

The impact of the harmful gas NO on the atmospheric environment cannot be ignored, so it is necessary to develop efficient gas sensors to detect and absorb NO at room temperature. In this work, we systematically explored the electron transport properties and gas sensing properties of Fe3GeTe2, In2Se3 monolayers and its multiferroic van der Waals (vdW) heterostructures of Fe3GeTe2/In2Se3 for detecting NO by using density functional theory and nonequilibrium Green's function methods. The calculated adsorption energies, electron localisation functions, band structures and density of states indicate that its a chemisorption for the adsorption of NO on Fe3GeTe2 and a physisorption on In2Se3, while the specific adsorption style is highly dependent on the stacking and molecular adsorption sites of different Fe3GeTe2/In2Se3 structures. In addition, the pristine Fe3GeTe2 monolayer and Fe3GeTe2/In2Se3 based nanodevices realized a significant anisotropy for electron transport along the zigzag and armchair directions, and their anisotropic maximum current ratios in the zigzag to armchair directions were 1.90 and 1.89. Meanwhile, the NO sensitivity ratio of Fe3GeTe2 and Fe3GeTe2/In2Se3 based gas sensors can be up to 79 % and 107 %, respectively. This highlights a notably superior gas-sensitive performance of the Fe3GeTe2/In2Se3 heterostructure compared to the Fe3GeTe2 monolayer gas devices. These findings provide valuable references for the application of multiferroic heterostructures in the field of gas sensors.

Rapid Transport of Energetic Electrons to Low L $L$‐Shells: The Key Role of Electric Fields

AbstractThe dynamics of the outer radiation belt are traditionally associated with wave‐particle resonant interactions, which provide local electron acceleration and losses through very low‐frequency waves, and electron radial transport by ultra‐low frequency waves. However, these processes cannot explain observations of rapid radial transport of energetic electrons (on a time‐scale of a couple of hours), deep into the inner magnetosphere (down to , mapping to magnetic latitude in the ionosphere). This transport is likely associated with strong convection electric fields forming around the plasmapause. To investigate these rapid, low‐latitude electron transport, we combine low‐altitude observations of energetic electron fluxes by the ELFIN CubeSats and DMSP satellites, SuperDARN measurements of ionospheric plasma flows (electric fields), and equatorial measurements of energetic electrons and electric fields by THEMIS. Our findings demonstrate that the rapid filling of the slot region by keV electrons is directly associated with electric field penetration to low latitudes (down to ). The proposed electron transport scenario, the direct penetration of energetic electrons by strong, localized electric fields, underscores the importance of ionosphere‐magnetosphere coupling in radiation belt dynamics.

Probing the two-electron-interaction-induced three new hopping processes in a double quantum-dot system revealed by finite-frequency shot noise

In the serially coupled double quantum dot (DQD) system, the two-electron-interaction-induced electron hopping processes and spin-exchange hopping processes play a crucial role in manipulating the spin degree of freedom of localized electrons in the DQD system. Consequently, from the perspective of electron transport, how to detect the new hopping processes induced by the two-electron interaction has become an increasingly important issue. Here, the influences of the three new hopping processes predicted by the generalized Hubbard model on the finite-frequency shot noise of electron transport through a serially coupled DQD system are studied. It is demonstrated that in the energy-level detuning case the criterion for the existence of the electron-occupation-modulated hopping processes is that the maximum number of peaks and dips of the finite-frequency shot noise equals eight while in the energy-level alignment case the criteria for the existence of the two-electron-interaction-induced three new hopping processes, and the antiparallel-electron-spin-exchange hopping and electron-pair hopping processes, and the electron-occupation-modulated hopping processes are that the maximum numbers of peaks and dips equal eight, seven, and six, respectively. Therefore, these results provide an alternative way to detect the three new hopping processes predicted by the generalized Hubbard model in the serially coupled DQD system.

SAT solver-driven approach for validating local electron counting rule

Determining large, complex surface structures is essential for understanding and modeling crystal growth. For semiconductor surfaces, the electron counting (EC) rule is known to be useful for predicting surface stability. In this study, a scheme is proposed to automatically determine if a sampled surface structure locally satisfies the EC rule using a Boolean Satisfiability Problem (SAT) solver. This automatic determination is demonstrated on the GaN(0001)-(6 × 6) surface system with H and Ga adsorption as an example. The scheme is also applicable to the automatic generation of surface structures that are expected to be relatively stable, and is expected to accelerate the study of large and complex surface structures of various semiconductor materials.

Unraveling the exceptional kinetics of Zn||organic batteries in hydrated deep eutectic solution

Intuitively, the solvation structure featuring stronger interacted sheath in deep eutectic solution (DES) electrolyte would result in sluggish interfacial charge transfer and intense polarization, which obstructs its practical application in emerging Zn based batteries. Unexpectedly, here we discover a Zn||organic battery with exceptional kinetics properties enabled by a hydrated DES electrolyte, which can render higher discharge capacity, smaller voltage polarization, and faster kinetics of charge transfer in comparison with conventional aqueous 3 M ZnCl2 electrolyte, though its viscosity is two orders of magnitude higher than the latter. The improved kinetics of charge transfer and ion diffusion is demonstrated to originate from the local electron structure regulation of cathode in hydrated DES electrolyte. Furthermore, the DES electrolyte has also been shown to restrict parasitic reaction associated with active water by preferential urea-molecular adsorption on Zn surface and stronger water trapping in solvation structure, giving rise to long-term stable dendrite-free Zn plating/stripping. This work provides a new rationale for understanding electrochemical behaviors of organic cathodes in DES electrolyte, which is conducive to the development of high-performance Zn||organic batteries.