Electron-electron Interaction Research Articles

Probing photoinduced electron transfer events in phenylferrocene-corrole dyad.

Herein, we investigated PhFC (10-phenylferrocenyl-5,15-diphenyl corrole), a corrole-based donor-acceptor (D-A) dyad, to understand the energy/electron transfer reaction dynamics. Phenylferrocene acts as the donor moiety when attached to the meso position of the corrole ring in the PhFC D-A system. The photophysical properties of the PhFC dyad and its parent molecule, TPC (5,10,15-triphenyl corrole), were studied by UV-vis spectroscopy, steady state fluorescence spectroscopy, TCSPC and optical microscopy techniques. A slight red shift and broadening of both the Q-band and Soret bands are observed in the absorption spectra of the PhFC dyad in comparison to TPC, representing the weak electronic interaction between the phenylferrocene moiety and corrole ring. The fluorescence emission spectrum of the PhFC dyad is significantly quenched (>80%) in comparison to TPC, attributed to the photoinduced electron transfer (PET) from phenylferrocene to the corrole ring. We observed that the electron transfer rate in the PhFC system is solvent dependent. Our theoretical investigation supported the experimental findings on the electron transfer mechanism. The HOMO and LUMO arrangements of these PhFC dyads demonstrate the electron density distribution and the ability of the donor moieties to transfer electrons to the corrole moiety. Fluorescence lifetime imaging microscopy (FLIM) was used to image the homogeneous lifetime distribution of the PhFC dyad and TPC.

Yu-Shiba-Rusinov bands in a self-assembled kagome lattice of magnetic molecules

Kagome lattices constitute versatile platforms for studying paradigmatic correlated phases. While molecular self-assembly of kagome structures on metallic substrates is promising, it is challenging to realize pristine kagome properties because of hybridization with the bulk degrees of freedom and modified electron-electron interactions. We suggest that a superconducting substrate offers an compelling platform for realizing a magnetic kagome lattice. Exchange coupling induces kagome-derived bands at the interface, which are protected from the bulk by the superconducting energy gap. We realize a magnetic kagome lattice on a superconductor by depositing Fe-porphin-chloride molecules on Pb(111) and using temperature-activated de-chlorination and self-assembly. This allows us to control the formation of smaller kagome precursors and long-range ordered kagome islands. Using scanning tunneling microscopy and spectroscopy at 1.6 K, we identify Yu-Shiba-Rusinov states inside the superconducting energy gap and track their hybridization from the precursors to larger islands, where the kagome lattice induces extended YSR bands. These YSR-derived kagome bands inside the superconducting energy gap allow for long-range coupling and induced pairing correlations, motivating further studies to resolve possible spin-liquid or Kondo-lattice-type behavior.

TD-DMRG Study of Exciton Dynamics with both Thermal and Static Disorders for Fenna-Matthews-Olson Complex.

Photosynthesis is a fundamental process that converts solar energy into chemical energy. Understanding the microscopic mechanisms of energy transfer in photosynthetic systems is crucial for the development of novel optoelectronic materials. Simulating these processes poses significant challenges due to the intricate interactions between electrons and phonons, compounded by static disorder. In this work, we present a numerically nearly exact study using the time-dependent density matrix renormalization group (TD-DMRG) method to simulate the quantum dynamics of the Fenna-Matthews-Olson (FMO) complex considering an eight-site model with both thermal and static disorders. We employ the thermo-field dynamics formalism for temperature effects. We merge all electronic interactions into one large matrix product state (MPS) site, boosting accuracy efficiently without increasing complexity. Previous combined experimental and computational studies indicated that the static disorders range from 30 to 90 cm-1 for different FMO sites. We employ a Gaussian distribution and the auxiliary bosonic operator approach to consider the static disorder in our TD-DMRG algorithm. We investigate the impact of different initial excitation sites, temperatures, and degrees of static disorder on the exciton dynamics and temporal coherence. It is found that under the influence of the experimentally determined static disorder strength, the exciton population evolution shows a non-negligible difference at zero temperature, while it is hardly affected at room temperature.

Conductive Zeolite Supported Indium-Tin Alloy Nanoclusters for Selective and Scalable Formic Acid Electrosynthesis.

Upgrading excess CO2 toward the electrosynthesis of formic acid is of significant research and commercial interest. However, simultaneously achieving high selectivity and industrially relevant current densities of CO2-to-formate conversion remains a grand challenge for practical implementations. Here, an electrically conductive zeolite support is strategically designed by implanting Sn ions into the skeleton structure of a zeolite Y, which impregnates ultrasmall In0.2Sn0.8 alloy nanoclusters into the supercages of the tailored 12-ring framework. The prominent electronic and geometric interactions between In0.2Sn0.8 nanoalloy and zeolite support lead to the delocalization of electron density that enhances orbital hybridizations between In active site and *OCHO intermediate. Thus, the energy barrier for the rate-limiting *OCHO formation step is reduced, facilitating the electrocatalytic hydrogenation of CO2 to formic acid. Accordingly, the developed zeolite electrocatalyst achieves an industrial-level partial current density of 322mA cm-2 and remarkable Faradaic efficiency of 98.2% for formate production and stably maintains Faradaic efficiency above 93% at an industrially relevant current density for over 102 h. This work opens up new opportunities of conductive zeolite-based electrocatalysts for industrial-level formic acid electrosynthesis from CO2 electrolysis and toward practically accessible electrocatalysis and energy conversion.

Electron-driven molecular processes for cyanopolyacetylenes HC2n+1N (n = 3, 4, and 5).

Linear carbon series cyanopolyacetylenes (HC2n+1N) (n = 3, 4, and 5) are astromolecules found in the atmosphere of Titan and interstellar media such as TMC-1 (Taurus molecular cloud-1). All these compounds are also detected in IRC + 10 216. In the present work, we comprehensively investigate electron interaction with important cyanopolyacetylene compounds, viz. HC7N (cyano-tri-acetylene), HC9N (cyano-tetra-acetylene), and HC11N (cyano-penta-acetylene). The study covers incident electron energies ranging from the ionization threshold to 5 keV. Various electron-driven molecular processes are quantified in terms of total cross-sections. The quantum spherical complex optical potential (SCOP) is used to determine elastic (Qel) and inelastic (Qinel) cross-sections. Ionization is the most important inelastic effect that opens various chemical pathways for the generation of different molecular species; we computed the ionization cross-section (Qion) and discrete electronic excitation cross-section (ΣQexc) using the complex scattering potential-ionization contribution (CSP-ic) method. The cyanopolyacetylene compounds are difficult to handle experimentally owing to the health risks involved. Therefore, there are no prior experimental data available for these molecules; only Qion have been reported theoretically. Thus, the present work is the maiden report on computing Qel, Qinel, ΣQexc, and QT. In order to provide an alternative approach and further validation of the present work, we employed our recently developed two-parameter semi-empirical method (2p-SEM) to compute Qel and QT. Additionally, we predict the polarizability of the HC11N molecule, which has not been reported in the existing literature. This prediction is based on a correlation study of polarizabilities of molecules with Qion values from the same series of molecules.

Introducing a new correlation functional in density functional theory

The correlation functional holds significance in density functional theory as it addresses electron–electron interactions beyond the mean-field approximation, enhancing the accuracy of total energy calculations, electronic excitations, and the prediction of materials properties. There are several expressions to describe this energy, and each of them has a unique set of errors in calculating particular properties of materials. This work offers a new correlation functional by employing the density's dependence on ionization energy. We theoretically derived this functional and combined it with the previously reported ionization energy dependent exchange functional to investigate its effect on the total energy, bond energy, dipole moment, and zero-point energy of 62 molecules. The comparison of this new functional in respect to existing widely used correlation models including QMC, PBE, B3LYP and Chachiyo models shows how well it works in producing accurate results with minimal mean absolute error.

Evidence of electron interaction with an unidentified bosonic mode in superconductor CsCa2Fe4As4F2

The kink structure in band dispersion usually refers to a certain electron-boson interaction, which is crucial in understanding the pairing in unconventional superconductors. Here we report the evidence of the observation of a kink structure in Fe-based superconductor CsCa2Fe4As4F2 using angle-resolved photoemission spectroscopy. The kink shows an orbital selective and momentum dependent behavior, which is located at 15 meV below Fermi level along the Γ−M\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\Gamma -{{\\rm{{M}}}}$$\\end{document} direction at the band with dxz orbital character and vanishes when approaching the Γ−X\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\Gamma -{{\\rm{{X}}}}$$\\end{document} direction, correlated with a slight decrease of the superconducting gap. Most importantly, this kink structure disappears when the superconducting gap closes, indicating that the corresponding bosonic mode (~9±1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$9\\pm 1$$\\end{document} meV) is closely related to superconductivity. However, the origin of this mode remains unidentified, since it cannot be related to phonons or the spin resonance mode (~15 meV) observed by inelastic neutron scattering. The behavior of this mode is rather unique and challenges our present understanding of the superconducting paring mechanism of the bilayer FeAs-based superconductors.

Design, synthesis, anti-cancer, anti-inflammatory and in silico studies of 3-substituted-2-oxindole derivatives.

This study focuses on the design and multistep synthesis of diverse structural and functional 3-substituted-2-oxindole derivatives aimed at beingdual-active molecules with anti-cancer and anti-inflammatory properties. In vitro evaluations confirmed the dualactivity of these derivatives.4a exhibited GI50 value 3.00E-05 against MDA-MB-231; 4b has shown GI50 value 2E-05 against MDA-MB-231; 4c has shown GI50 value 6E-05 against VERO; and4d has shown GI50 value 8E-05 each against both MDA-MB-231 and MCF-7. 4e has shown GI50 values 2E-05 and 5E-05 each against both the MCF-7 and VERO. The analysis indicates that compounds 3c (71.19%), 3e (66.84%), and 3g (63.04%) exhibited significant anti-inflammatory activity. Additionally, in silico binding free energy analysis and interaction studies revealed significant correlations between in vitro and computational data, identifying compounds 4d, 4e, 3b, 3i, and 3e as promising candidates. Key residues such as Glu917, Cys919, Lys920, Glu850, Lys838, and Asp1046 were found to play critical roles in ligand binding and kinase inhibition, providing valuable insights for designing potent VEGFR2 inhibitors. The quantum mechanics-based independent gradient model analysis further highlighted the electronic interaction landscape, showing larger attractive peaks and higher electron density gradients for compounds 4d and 4e compared to Sunitinib, suggesting stronger and diverse attractive forces.

Unveiling the Enhancement of Electrocatalytic Oxygen Evolution Activity in Ru-Fe2O3/CoS Heterojunction Catalysts.

The development of highly efficient electrocatalysts for the sluggish anodic oxygen evolution reaction (OER) is crucial to meet the practical demand for water splitting. In this study, an effective approach is proposed that simultaneously enhances interfacial interaction and catalytic activity bymodifyingFe2O3/CoS heterojunctionusing Ru doping strategy to construct an efficient electrocatalytic oxygen evolution catalyst. The unique morphology of Ru doped Fe2O3 (Ru-Fe2O3) nanoring decorated by CoS nanoparticles ensures a large active surface area and a high number of active sites. The designed Ru-Fe2O3/CoS catalyst achieves a low OER overpotential (264mV) at 10mAcm-2 and demonstrates exceptional stability even at high current density of 100mAcm-2, maintaining its performance for an impressive duration of 90h. The catalytic performance of this Ru-Fe2O3/CoS catalyst surpasses that of other iron-based oxide catalysts and even outperforms the state-of-the-art RuO2. Density functional theory (DFT) calculation as well as experimental in situ characterization confirm that the introduction of Ru atoms can enhance the interfacial electron interaction, accelerating the electron transfer, and serve as highly active sites reducing the energy barrier for rate determination step. This work provides an efficient strategy to reveal the enhancement of electrocatalytic oxygen evolution activity of heterojunction catalysts by doping engineering.

Understanding the Nonlinear Hammett Relationship in Osmylation of Olefins with OsO4-Amine Ligands: Importance of Singlet-Diradical Character.

Although the concerted [3 + 2] mechanism of osmium-catalyzed asymmetric dihydroxylation has been generally accepted, the unusual nonlinear Hammett relationship induced by amine-type ligands remains unexplained. To understand this, we carried out a density functional theory (DFT) study for the osmylation of substituted styrenes by the following: OsO4, OsO4-pyridine, OsO4-4-cyanopyridine, OsO4-4-pyrrolidinopyridine, and OsO4-quinuclidine. Calculations using the M06 functional successfully reproduce the experimentally observed nonlinear relationships. The transition states exhibit considerable singlet-diradical character, which causes the nonlinear Hammett relationship. Regardless of the presence or absence of an amine-type ligand, an electron donation from styrene to OsO4 is observed, indicating no mechanistic change. Calculations indicate that the electronic interaction between the amine-type ligand and styrene also influences the reaction rate.

Direct observation of the electronic structure and many-body interactions of low-mobility carriers in perylene diimide derivative

Despite the rapid progresses in the field of organic semiconductors, aided by the development of high-mobility organic materials, their high carrier mobilities are often unipolar, being sufficiently high only for either electrons or holes. Yet, the basic mechanisms underlying such significant mobility asymmetry largely remains elusive. We perform angle-resolved photoelectron spectroscopy to reveal the occupied band structures and the many-body interactions for low-mobility hole carriers in a typical n-type semiconductor perylene diimide derivative. The band dispersion exhibits strong renormalization to the calculated non-interacting electronic structure. The analysis including many-body interactions elucidate that the significant mass enhancement can be understood in terms of strong charge–phonon coupling, leading to an important mechanism of polaron band transport of low intrinsic carrier mobility in organic semiconductors.

Enhanced Efficiency of Solar Wind Electron Interaction with Whistlers Caused by Switchback-related Magnetic Dips

Through test particle simulations based on solar wind observations by the Parker Solar Probe (PSP) mission, we demonstrate that a magnetic gradient can significantly enhance the efficiency of scattering and energization of the strahl electrons by quasi-parallel whistlers, through the phase trapping effect due to the gyrosurfing mechanism. We identify quasi-linear and nonlinear regimes of these interactions for different combinations of wave amplitude (B w /B 0) and the strength of the magnetic field gradient with magnetic field depletion level (B h /B 0) as a proxy. Nonlinear effects are observed for B w /B 0 ≳ 10−3 and B h /B 0 ≳ 0.1. We estimated the extending of the resonant energy range due to the wave and the magnetic field gradient interplay and demonstrated that these mechanisms result in the broadening of the strahl electron pitch-angle distribution typically observed in situ. The combination of parallel whistlers collocated with a magnetic gradient is frequently observed by PSP in magnetic dips at the edges of magnetic switchbacks. Our results indicate that these mechanisms may be highly relevant for pitch-angle scattering of the strahl electrons and regulating the heat flux near the Sun at heliocentric distances of 30–45 R S . Specifically, core and halo electrons may experience a 10% increase in their initial energy, and the majority of strahl electrons may be scattered (by an average of 30°) into the hot and trapped plasma inside magnetic dips.

Octahedral Hexanuclear Rhenium Cluster Dimers Bridged by Pyrazine or 4,4'-Bipyridine with 23- and 24-Electron Configurations.

New pyrazine (pz)- and 4,4'-bipyridine (4,4'-bpy)-bridged octahedral hexanuclear rhenium(III) cluster dimers, [{Re6(μ3-S)8Cl5}2(μ-L)]6- (L = pz, [1]6-; L = 4,4'-bpy, [2]6-), with 2 × 24 d-electrons {Re6(24e)}2 were obtained in a single-step reaction via photoirradiation of [Re6(μ3-S)8Cl6]4- with L in a 2:1 ratio at room temperature. The {Re6(23e)}2 dimers, [{Re6(μ3-S)8Cl5}2(μ-L)]4- (L = pz, [1']4-; L = 4,4'-bpy, [2']4-), were synthesized through two-electron oxidation of [1]6- and [2]6-, respectively. The single-crystal X-ray structures of [1]6- and [1']4- were determined, revealing structural distortion of the Re6 core of [1']4- due to the Jahn-Teller effect. The cyclic voltammograms of [1]6- and [2]6- showed two steps of one-electron redox processes attributable to Re6(23e)Re6(24e)/{Re6(24e)}2 and {Re6(23e)}2/Re6(23e)Re6(24e), respectively. The separation between the two redox potentials is small (0.056 V for [1]6- and 0.039 V for [2]6-). The magnetic susceptibilities of [1']4- and [2']4- were almost temperature-independent, with values of 2.98 and 2.85 μB, respectively, indicating paramagnetism. These results suggest weak electronic interaction between two cluster units bridged by pz or 4,4'-bpy in the intercluster mixed valence state. The compounds [1]6- and [2]6- show photoluminescence in the near-infrared region at 296 K in the solid state.

Iron-cobalt phosphide/nitrogen-doped carbon composite derived from prussian blue analogues as anode materials for sodium-ion batteries

Transition metal phosphides (TMPs) are recognized as attractive substitutes for lithium/sodium storage owing to their notable capacity and outstanding safety features. However, they face significant challenges in applications, particularly poor cycling stability and rapid capacity decay. In this study, we report a simple strategy utilizing dopamine-coated Prussian blue analogues as precursors to prepare bimetallic iron‑cobalt phosphide/nitrogen-doped carbon (Fe1-xCoxP/NC) composite materials via a one-step carbothermal phosphorization process. Benefiting from their nanostructured advantages and electronic interactions between Fe and Co sites, Fe0.17Co0.83P/NC, prepared by adjusting and optimizing the ion ratio, exhibits excellent rate capability and cycling performance as an anode material for sodium-ion batteries. It achieves a high specific capacity of 505.6 mAh g−1 at 0.5 A g−1. Even after 1000 cycles at a high current of 1 A g−1, the reversible specific capacity remains at 413.6 mAh g−1. Ex-situ XRD studies confirm that Fe0.17Co0.83P/NC stores Na+ via a conversion mechanism, where the crystalline CoP phase transforms into Na3P phase during the discharging process.

Accelerated Electron-Hole Separation at the Organic-Inorganic Anthracene/Janus MoSSe Interface.

Organic light-absorbing materials with two-dimensional semiconductor layers as contact electrodes are promising for efficient and flexible low-cost solar cells. Considering anthracene as an absorber and a MoSSe Janus monolayer, we use non-adiabatic molecular dynamics to show that electron transfer from anthracene to MoSSe is faster on the Se side than the S side. The transfer from anthracene to MoS2 and MoSe2 monolayers takes intermediate times. As a rule, we find that a shorter adsorption distance produces a stronger donor-acceptor coupling. The smaller distance on the Se side is rationalized by the attractive force between the intrinsic dipole moment of the Janus structure and that of the molecule induced due to adsorption. Quantum coherence also affects the transfer time. The study provides detailed insights into adsorption of molecules on Janus structures and the resulting electronic and electron vibrational interactions. The results suggest that the dipole interaction plays an important role in the thermodynamic stability, alignment of electronic levels, and electron vibrational dynamics.

Emergent phases in graphene flat bands.

Electronic correlations in two-dimensional materials play a crucial role in stabilising emergent phases of matter. The realisation of correlation-driven phenomena in graphene has remained a longstanding goal, primarily due to the absence of strong electron-electron interactions within its low-energy bands. In this context, magic-angle twisted bilayer graphene has recently emerged as a novel platform featuring correlated phases favoured by the low-energy flat bands of the underlying moiré superlattice. Notably, the observation of correlated insulators and superconductivity has garnered significant attention, leading to substantial progress in theoretical and experimental studies aiming to elucidate the origin and interplay between these two phases. A wealth of correlated phases with unprecedented tunability was discovered subsequently, including orbital ferromagnetism, Chern insulators, strange metallicity, density waves, and nematicity. However, a comprehensive understanding of these closely competing phases remains elusive. The ability to controllably twist and stack multiple graphene layers has enabled the creation of a whole new family of moiré superlattices with myriad properties being discovered at a fast pace. Here, we review the progress and development achieved so far, encompassing the rich phase diagrams offered by these graphene-based moiré systems. Additionally, we discuss multiple phases recently observed in non-moiré multilayer graphene systems. Finally, we outline future opportunities and challenges for the exploration of hidden phases in this new generation of moiré materials.

Third-order nonlinear Hall effect in a quantum Hall system.

In two-dimensional systems, perpendicular magnetic fields can induce a bulk band gap and chiral edge states, which gives rise to the quantum Hall effect. The quantum Hall effect is characterized by zero longitudinal resistance (Rxx) and Hall resistance (Rxy) plateaus quantized to h/(υe2) in the linear response regime, where υ is the Landau level filling factor, e is the elementary charge and h is Planck's constant. Here we explore the nonlinear response of monolayer graphene when tuned to a quantum Hall state. We observe a third-order Hall effect that exhibits a nonzero voltage plateau scaling cubically with the probe current. By contrast, the third-order longitudinal voltage remains zero. The magnitude of the third-order response is insensitive to variations in magnetic field (down to ~5 T) and in temperature (up to ~60 K). Moreover, the third-order response emerges in graphene devices with a variety of geometries, different substrates and stacking configurations. We term the effect third-order nonlinear response of the quantum Hall state and propose that electron-electron interaction between the quantum Hall edge states is the origin of the nonlinear response of the quantum Hall state.

Tunnel transport problem for open multilayer nitride nanostructures with an applied constant magnetic field and time-dependent potential: An exact solution

A quantum mechanical theory for description of electronic quasistationary states in two-dimensional (2D) layered semiconductor nanostructure was developed. A constant external magnetic field B was directed along semiconductor layers. The presence of internal electric fields F originated from the potential barriers and wells in semiconductor layers was taken into account. The vector of F was directed perpendicularly to semiconductor layers. The interaction of tunneled electrons with a time-dependent electromagnetic fields was analyzed in detail. An approach to obtain an exact solution to the problem based on a combination of the Lewis-Riesenfeld method for complete Schrödinger equation and scattering theory was developed. Application of the scattering theory in combination with the -matrix and transfer-matrix methods allowed us to calculate the electron quasistationary spectra. Effects of magnetic field on the resonant energy and width of electronic quasistationary states as well as on the electronic conductivity were also discussed. Published by the American Physical Society 2024

Oxygen Vacancy Enabled Electronic Structure Engineering of Pt-WO3 Nanosheets toward Highly Efficient BTEX Sensing.

A Pt nanoparticle-immobilized WO3 material is a promising candidate for catalytic reactions, and the surface and electronic structure can strongly affect the performance. However, the effect of the intrinsic oxygen vacancy of WO3 on the d-band structure of Pt and the synergistic effect of Pt and the WO3 matrix on reaction performance are still ambiguous, which greatly hinders the design of advanced materials. Herein, Pt-decorated WO3 nanosheets with different electronic metal-support interactions are successfully prepared by finely tuning the oxygen vacancy structure of WO3 nanosheets. Notably, Pt-modified WO3 nanosheets annealed at 400 °C exhibit excellent benzene series (BTEX) sensing performance (S = 377.33, 365.21, 348.45, and 319.23 for 50 ppm ethylbenzene, benzene, toluene, and xylene, respectively, at 140 °C), fast response and recovery dynamics (10/7 s), excellent reliability (σ = 0.14), and sensing stability (φ = 0.08%). Detailed structural characterization and DFT results reveal that interfacial Ptδ+-Ov-W5+ sites are recognized as the active sites, and the oxygen vacancies of the WO3 matrix can significantly affect the d-band structure of Pt nanoparticles. Notably, Pt/WO3-400 with improved surface oxygen mobility and medium electronic metal-support interaction facilitates the activation and desorption of BTEX, which contributes to the highly efficient BTEX sensing performance. Our work provides a new insight for the design of high-performance surface reaction materials for advanced applications.

Modeling Electron Energy Loss and Momentum Transfer in a Swift Electron Interaction with Small Polyhedral Nanoparticles

Modeling Electron Energy Loss and Momentum Transfer in a Swift Electron Interaction with Small Polyhedral Nanoparticles