The Electronic Structures and Catalytic Activities of Triruthenium Ketenylidene Clusters Supported on Oxides

he catalytic activities of [H_nRu_3(CO)_9(CCO)]￣(-(2-n)) (n=0, 1 , 2 , 3) support-ed on oxides have been estimated using INDO calculations and correlation betweencatalytic activity and electronic structure for these clusters have been established.The activity in ￣(13)CO isotopic exchange strongly relates to the bond orders of Ru-CO and C-CO, and the activity in alkylation with nucleophile or electrophile de-pends mainly on the net charges at Ca atoms. In addition, the possible species of[H_3Ru_3(CO)_9(CCO)]￣+ has been proposed although it has not been synthesized upto now.

Tuning electronic structure of RuO_(2)by single atom Zn and oxygen vacancies to boost oxygen evolution reaction in acidic medium

The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.

Rational modulation of electronic structure in PtAuCuNi alloys boosts efficient electrocatalytic ethanol oxidation assisted with energy-saving hydrogen evolution

Compared to conventional electrocatalytic water splitting,electrocatalytic ethanol oxidation reaction(EOR)along with hydrogen production is considered a more energy-efficient strategy.Herein,we prepared a type of novel quaternary alloy catalyst(PtAuCuNi@NF)that exhibits excellent activity for EOR(0.215 V at 10 mA cm^(-2))and hydrogen evolution reaction(HER)(7 mV at 10 mA cm^(-2)).Experimental results demonstrated that both Cu and Ni modulated the electronic environment around Pt and Au.The electron-rich active center facilitates the rapid adsorption and dissociation of reactants and intermediates for both EOR and HER.Impressively,in the ethanol-assisted overall water splitting(E-OWS),a current density of 10 mA cm^(-2)was achieved at 0.28 V.Moreover,an advanced acid-base self-powered system(A-Bsps)that can achieve a self-powered voltage of 0.59 V was assembled.Accordingly,the self-driven hydrogen production with zero external power supply was realized by integrating A-Bsps with the E-OWS equipment.The interesting results can provide a feasible strategy for designing and developing advanced nanoalloy-based materials for clean energy integration and use in various fields.

Tuning the surface electronic structure of noble metal aerogels to promote the electrocatalytic oxygen reduction

The sluggish kinetics of the oxygen reduction reaction(ORR)is the bottleneck for various electrochemical energy conversion devices.Regulating the electronic structure of electrocatalysts by ligands has received particular attention in deriving valid ORR electrocatalysts.Here,the surface electronic structure of Ptbased noble metal aerogels(NMAs)was modulated by various organic ligands,among which the electron-withdrawing ligand of 4-methylphenylene effectively boosted the ORR electrocatalysis.Theoretical calculations suggested the smaller energy barrier for the transformation of O^(*) to OH^(*) and downshift the d-band center of Pt due to the interaction between 4-methylphenylene and the surface metals,thus enhancing the ORR intrinsic activity.Both Pt3Ni and Pt Pd aerogels with 4-methylphenylene decoration performed significant enhancement in ORR activity and durability in different media.Remarkably,the 4-methylphenylene modified Pt Pd aerogel exhibited the higher halfwave potential of 0.952 V and the mass activity of 10.2 times of commercial Pt/C.This work explained the effect of electronic structure on ORR electrocatalytic properties and would promote functionalized NMAs as efficient ORR electrocatalysts.

Electronic structure and spin state regulation of vanadium nitride via a sulfur doping strategy toward flexible zinc-air batteries

Owing to the distinctive structural characteristics,vanadium nitride(VN)is highly regarded as a catalyst for oxygen reduction reaction(ORR)in zinc-air batteries(ZABs).However,VN exhibits limited intrinsic ORR activity due to the weak adsorption ability to O-containing species.Here,the S-doped VN anchored on N,S-doped multi-dimensional carbon(S-VN/Co/NS-MC)was constructed using the solvothermal and in-situ doping methods.Incorporating sulfur atoms into VN species alters the electron spin state of vanadium in the S-VN/Co/NS-MC for regulating the adsorption energy of vanadium sites to oxygen molecules.The introduced sulfur atoms polarize the V 3d_(z)^(2) electrons,shifting spin-down electrons closer to the Fermi level in the S-VN/Co/NS-MC.Consequently,the introduction of sulfur atoms into VN species enhances the adsorption energy of vanadium sites for oxygen molecules.The*OOH dissociation transitions from being unspontaneous on the VN surface to a spontaneous state on the S-doped VN surface.Then,the ORR barrier on the S-VN/Co/NS-MC surface is reduced.The S-VN/Co/NS-MC demonstrates a higher half-wave potential and limiting current density compared to the VN/Co/N-MC.The S-VN/Co/NS-MC-based liquid ZABs display a power density of 195.7 m W cm^(-2),a specific capacity of 815.7 m A h g^(-1),and a cycling stability exceeding 250 h.The S-VN/Co/NS-MC-based flexible ZABs are successfully employed to charge both a smart watch and a mobile phone.This approach holds promise for advancing the commercial utilization of VN-based catalysts in ZABs.

Mechanical Properties and Electronic Structures of M(M=Ti,V,Cr,Mn and Fe)Dopedβ-Si_(3)N_(4) from First-Principle

The structures,mechanical properties and electronic structures of M metals(M=Ti,V,Cr,Mn and Fe)dopedβ-Si_(3)N_(4) were investigated by First-principles calculations within CASTEP.The calculated lattice parameters ofβ-Si_(3)N_(4) were consistent with previous date.The cohesive energy and formation enthalpy show that initialβ-Si_(3)N_(4) has the highest structural stability.The calculated elastic constant and the Voigt-Reuss-Hill approximation indicate that elastic moduli ofβ-Si_(3)N_(4) are slightly reduced by M doping.Based on Poisson’s and Pugh’s ratio,β-Si_(3)N_(4) is a ductile material and the toughness ofβ-Si_(3)N_(4) increases with M doping,and Fe doping exhibited the best toughness.The results of density of states,charge distributions and overlapping populations indicate thatβ-Si_(3)N_(4) has the strong covalent and ionic bond strength between N and Si.

Geometries and electronic structures of Zr_(n)Cu(n=2–12) clusters: A joint machine-learning potential density functional theory investigation

Zr-based amorphous alloys have attracted extensive attention because of their large glassy formation ability, wide supercooled liquid region, high elasticity, and unique mechanical strength induced by their icosahedral local structures.To determine the microstructures of Zr–Cu clusters, the stable and metastable geometry of Zr_(n)Cu(n=2–12) clusters are screened out via the CALYPSO method using machine-learning potentials, and then the electronic structures are investigated using density functional theory. The results show that the Zr_(n)Cu(n ≥ 3) clusters possess three-dimensional geometries, Zr_(n)Cu(n≥9) possess cage-like geometries, and the Zr_(12)Cu cluster has icosahedral geometry. The binding energy per atom gradually gets enlarged with the increase in the size of the clusters, and Zr_(n)Cu(n=5,7,9,12) have relatively better stability than their neighbors. The magnetic moment of most Zr_(n)Cu clusters is just 1μB, and the main components of the highest occupied molecular orbitals(HOMOs) in the Zr_(12)Cu cluster come from the Zr-d state. There are hardly any localized two-center bonds, and there are about 20 σ-type delocalized three-center bonds.

Electronic structure and effective mass of pristine and Cl-doped CsPbBr_(3)

Organic–inorganic lead halide perovskites(LHPs) have attracted great interest owing to their outstanding optoelectronic properties.Typically,the underlying electronic structure would determinate the physical properties of materials.But as for now,limited studies have been done to reveal the underlying electronic structure of this material system,comparing to the huge amount of investigations on the material synthesis.The effective mass of the valance band is one of the most important physical parameters which plays a dominant role in charge transport and photovoltaic phenomena.In pristine CsPbBr_(3),the Fr?hlich polarons associated with the Pb–Br stretching modes are proposed to be responsible for the effective mass renormalization.In this regard,it would be very interesting to explore the electronic structure in doped LHPs.Here,we report high-resolution angle-resolved photoemission spectroscopy(ARPES) studies on both pristine and Cl-doped CsPbBr_(3).The experimental band dispersions are extracted from ARPES spectra along both ■ and ■ high symmetry directions.DFT calculations are performed and directly compared with the ARPES data.Our results have revealed the band structure of Cl-doped CsPbBr_(3) for the first time,which have also unveiled the effective mass renormalization in the Cl-doped CsPbBr_(3) compound.Doping dependent measurements indicate that the chlorine doping could moderately tune the renormalization strength.These results will help understand the physical properties of LHPs as a function of doping.

Structure,electronic,and nonlinear optical properties of superalkaline M_(3)O(M=Li,Na)doped cyclo[18]carbon

Cyclo[18]carbon has received considerable attention thanks to its novel geometric configuration and special electronic structure.Superalkalis have low ionization energy.Doping a superalkali in cyclo[18]carbon is an effective method to improve the optical properties of the system because considerable electron transfer occurs.In this paper,the geometry,bonding properties,electronic structure,absorption spectrum,and nonlinear optical(NLO)properties of superalkaline M_(3)O(M=Li,Na)-doped cyclo[18]carbon were studied by using density functional theory.M_(3)O and the C_(18) rings are not coplanar.The C_(18) ring still exhibits alternating long and short bonds.The charge transfer between M_(3)O and C_(18) forms stable[M_(3)O]+[C_(18)]-ionic complexes.C_(18)M_(3)O(M=Li,Na)shows striking optical nonlinearity,i.e.,their first-and second-order hyperpolarizability(βvec andγ||)increase considerably atλ=1907 nm and 1460 nm.

Tuning the electronic structure of a metal-organic framework for an efficient oxygen evolution reaction by introducing minor atomically dispersed ruthenium

The establishment of efficient oxygen evolution electrocatalysts is of great value but also challenging.Herein,a durable metal–organic framework(MOF)with minor atomically dispersed ruthenium and an optimized electronic structure is constructed as an efficient electrocatalyst.Significantly,the obtained NiRu_(0.08)-MOF with doping Ru only needs an overpotential of 187 mV at 10 mA cm^(-2) with a Tafel slop of 40 mV dec^(-1) in 0.1M KOH for the oxygen evolution reaction,and can work continuously for more than 300 h.Ultrahigh Ru mass activity is achieved,reaching 56.7 Ag^(-1)_(Ru) at an overpotential of 200 mV,which is 36 times higher than that of commercial RuO_(2).X-ray adsorption spectroscopy and density function theory calculations reveal that atomically dispersed ruthenium on metal sites in MOFs is expected to optimize the electronic structure of nickel sites,thus improving the conductivity of the catalyst and optimizing the adsorption energy of intermediates,resulting in significant optimization of electrocatalytic performance.This study could provide a new avenue for the design of efficient and stable MOF electrocatalysts.

Electronic structure study of the charge-density-wave Kondo lattice CeTe_(3)

The behaviors of f electrons are crucial for understanding the rich phase diagrams and ground-state properties of heavy fermion(HF)systems.The complicated interactions between f electrons and conduction electrons largely enrich the basic properties of HF compounds.Here the electronic structure,especially the f-electron character,of the charge-density-wave(CDW)Kondo lattice compound CeTe_(3)has been studied by high-resolution angle-resolved photoemission spectroscopy.A weakly dispersive quasiparticle band near the Fermi level has been observed directly,indicating hybridization between f electrons and conduction electrons.Temperature-dependent measurements confirm the localized to itinerant transition of f electrons as the temperature decreases.Furthermore,an energy gap formed by one conduction band at low temperature is gradually closed with increasing temperature,which probably originates from the CDW transition at extremely high temperature.Additionally,orbital information of different electrons has also been acquired with different photon energies and polarizations,which indicates the anisotropy and diverse symmetries of the orbitals.Our results may help understand the complicated f-electron behaviors when considering its interaction with other electrons/photons in CeTe_(3)and other related compounds.

Intrinsic electronic structure and nodeless superconducting gap of YBa_(2)Cu_(3)O_(7)-σ observed by spatially-resolved laser-based angle resolved photoemission spectroscopy

The spatially-resolved laser-based high-resolution angle resolved photoemission spectroscopy(ARPES) measurements have been performed on the optimally-doped YBa_(2)Cu_(3)O_(7)-σ(Y123) superconductor. For the first time, we found the region from the cleaved surface that reveals clear bulk electronic properties. The intrinsic Fermi surface and band structures of Y123 were observed. The Fermi surface-dependent and momentum-dependent superconducting gap was determined which is nodeless and consistent with the d+is gap form.

Pressure-induced phase transition and electronic structure evolution in layered semimetal HfTe_(2)

Motivated by the recent experimental work,the pressure-induced structural transition of well-known two-dimensional(2D)1T-Hf Te_(2)was investigated up to 50 GPa through the advanced CALYPSO structure search technique combined with the first-principles calculations.Our calculations suggested that the 1T-Hf Te_(2)will first transform to C2/m phase at 3.6 GPa with a volume reduction of 7.6%and then to P62m phase at 9.6 GPa with a volume collapse of 4.6%.The occurrences of 3D C2/m and P62m phases mainly originated from the enhanced Te-Te interlayer coupling and the drastic distortions of Hf-Te polyhedrons in P3m1 phase under compression.Concomitantly,the coordination number of Hf atoms increased from six in P3m1 to eight in C2/m and eventually to nine in P62m at elevated pressure.The metallic and semimetallic nature of C2/m and P62m phases were characterized,and the evidence of the reinforced covalent interactions of Te-Hf and Te-Te orbitals in these two novel high-pressure phases were manifested by the atom-projected electronic DOS and Bader charge.

Probing electronic structures of transition metal complexes using electron paramagnetic resonance spectroscopy

Electron paramagnetic resonance(EPR)or electron spin resonance(ESR)has been widely employed to characterize transition metal complexes.However,because of the high degree of complexity of transition metal EPR spectra,how to extract the underlying electronicstructure information inevitably poses a major challenge to beginners,in particular for systems with S>1/2.In fact,the physical principles of transition metal EPR have long been well-established and since 1970s a series of dedicated voluminous monographs have been published already.Not surprisingly,they are not appropriate stating points for novices to grasp a panorama of the profound theory prior to scrutinizing in-depth references.The present review aims to fill this gap to provide a perspective of transition metal EPR and unveil some peculiar subtleties thereof on the basis of our recent work.

Study of the Electronic Structure and Optical Properties of Rare Earth Luminescent Materials

Rare earth luminescent materials have attracted significant attention due to their wide-ranging applications in the field of optoelectronics. This study aims to delve into the electronic structure and optical properties of rare earth luminescent materials, with the goal of uncovering their importance in luminescence mechanisms and applications. Through theoretical calculations and experimental methods, we conducted in-depth analyses on materials composed of various rare earth elements. Regarding electronic structure, we utilized computational techniques such as density functional theory to investigate the band structure, valence state distribution, and electronic density of states of rare earth luminescent materials. The results indicate that the electronic structural differences among different rare earth elements notably influence their luminescence performance, providing crucial clues for explaining the luminescence mechanism. In terms of optical properties, we systematically examined the material’s optical behaviors through fluorescence spectroscopy, absorption spectroscopy, and other experimental approaches. We found that rare earth luminescent materials exhibit distinct absorption and emission characteristics at different wavelengths, closely related to the transition processes of their electronic energy levels. Furthermore, we studied the influence of varying doping concentrations and impurities on the material’s optical properties. Experimental outcomes reveal that appropriate doping can effectively regulate the emission intensity and wavelength, offering greater possibilities for material applications. In summary, this study comprehensively analyzed the electronic structure and optical properties of rare earth luminescent materials, providing deep insights into understanding their luminescence mechanisms and potential value in optoelectronic applications. In the future, these research findings will serve as crucial references for the technological advancement in fields such as LEDs, lasers, and bioimaging.

Electronic structure of the SrAl_2O_4:Eu^(2+) persistent luminescence material

The electronic structure of the strontium aluminate （SrAl2O4：Eu^2＋） materials was studied with a combined experimental and theo- retical approach. The UV-VUV synchrotron radiation was applied in the experimental study while the electronic structure of the non-optimized and optimized crystal structure were investigated theoretically by using the density functional theory. The structure of the valence and conduction bands as well as the band gap energy of the material together with the position of the Eu2＋ 4f7 85712 ground state were calculated. The calculated band gap energy （6.4 eV） agreed well with the experimental value of 6.6 eV. The valence band consisted mainly of oxygen states whereas the bottom of the conduction band of strontium states. In agreement with the experimental results, the calculated 4f7 8S7r2 ground state of Eu2＋ lies in the energy gap of the host. The position of the 4f7 ground state depended on the Coulomb repulsion strength. The position of the 4f7 ground state with respect to the valence and conduction bands was discussed using theoretical and experimental evidence available.

First-principles study and electronic structures of Mn-doped ultrathin ZnO nanofilms

The first-principles density functional calculation is used to investigate the electronic structures and magnetic properties of Mn-doped and N-co-doped ZnO nanofilms.The band structure calculation shows that the band gaps of ZnO films with 2,4,and 6 layers are larger than the band gap of the bulk with wurtzite structure and decrease with the increase of film thickness.However,the four-layer ZnO nanofilms exhibit ferromagnetic phases for Mn concentrations less than 24% and 12% for Mn-doping performed in the whole layers and two layers of the film respectively,while they exhibit spin glass phases for higher Mn concentrations.It is also found,on the one hand,that the spin glass phase turns into the ferromagnetic one,with the substitution of nitrogen atoms for oxygen atoms,for nitrogen concentrations higher than 16% and 5% for Mn-doping performed in the whole layers and two layers of the film respectively.On the other hand,the spin-glass state is more stable for ZnO bulk containing 5% of Mn impurities,while the ferromagnetic phase is stable by introducing the p-type carriers into the bulk system.Moreover,it is shown that using the effective field theory for ferromagnetic system,the Curie temperature is close to the room temperature for the undamped Ruderman-Kittel-Kasuya-Yoshida（RKKY） interaction.

Phase stability,elastic properties and electronic structures of Mg-Y intermetallics from first-principles calculations

The phase stability,elastic properties and electronic structures of three typical Mg-Y intermetallics including Mg_(24)Y_(5),Mg_(2)Y and MgY are systematically investigated using first-principles calculations based on density functional theory.The optimized structural parameters including lattice constants and atomic coordinates are in good agreement with experimental values.The calculated cohesive energies and formation enthalpies show that either phase stability or alloying ability of the three intermetallics is gradually enhanced with increasing Y content.The single-crystal elastic constants C_(ij) of Mg-Y intermetallics are also calculated,and the bulk modulus B,shear modulus G,Young's modulus E,Poisson ratio v and anisotropy factor A of polycrystalline materials are derived.It is suggested that the resistances to volume and shear deformation as well as the stiffness of the three intermetallics are raised with increasing Y content.Besides,these intermetallics all exhibit ductile characteristics,and they are isotropic in compression but anisotropic to a certain degree in shear and stiffness.Comparatively,Mg_(24)Y_(5) presents a relatively higher ductility,while MgY has a relatively stronger anisotropy in shear and stiffness.Further analysis of electronic structures indicates that the phase stability of Mg-Y intermetallics is closely related with their bonding electrons numbers below Fermi level.Namely,the more bonding electrons number below Fermi level corresponds to the higher structural stability of Mg-Y intermetallics.

Atomic and electronic structures of montmorillonite in soft rock

Montmorillonite is a kind of clay mineral which often causes large deformation in soft-rock tunnel engineering and thus brings about safety problems in practice.To deal with these engineering safety problems,the physical and chemical properties of montmorillonite should be studied from basic viewpoints.We study the atomic and electronic structures of montmorillonite by using density-functional theory within the local-density approximation （LDA）.The results of calculation show that Al-O bond lengths are longer than Si-O bond lengths.It is found that both the valence band maximum （VBM） and the conduction band minimum （CBM） of montmorillonite are at point Г,and the calculated direct band gap of montmorillonite is 5.35 eV. We show that the chemical bonding between cations and oxygen anions in montmorillonite is mainly ionic,accompanied as well by a minor covalent component.It is pointed out that the VBM and CBM of montmorillonite consist of oxygen 2p and cation s states,respectively.Our calculated results help to understand the chemical and physical properties of montmorillonite,and are expected to be a guide for solving the problem of large deformation of soft-rock tunnels.

Electronic structure and optical properties of In-doped SrTiO3 by density function theory

The effect of In doping on the electronic structure and optical properties of SrTiO3 is investigated by the first-principles calculation of plane wave ultra-soft pseudo-potential based on the density function theory （DFT）. The calculated results reveal that due to the hole doping, the Fermi level shifts into valence bands （VBs） for SrTi1-x InxO3 with x = 0.125 and the system exhibits p-type degenerate semiconductor features. It is suggested according to the density of states （DOS） of SrTi0.875In0.125O3 that the band structure of p-type SrTIO3 can be described by a rigid band model. At the same time, the DOS shifts towards high energies and the optical band gap is broadened. The wide band gap, small transition probability and weak absorption due to the low partial density of states （PDOS） of impurity in the Fermi level result in the optical transparency of the film. The optical transmittance of In doped SrTiO3 is higher than 85% in a visible region, and the transmittance improves greatly. And the cut-off wavelength shifts into a blue-light region with the increase of In doping concentration.