Electronic Density Of States Research Articles

Electronic and photocatalytic properties of Cu4 cluster-modified Ag/g-C3N4 single-atom catalysts: A hybrid DFT study

Increasing the active sites on the catalyst surface has been a key goal to increase the catalyst efficiency. This paper presents an efficient conversion of solar energy into chemical energy, realized by a Cu4 cluster-assisted single-atom catalyst (Ag-doped g-C3N4). The catalyst enhances charge transfer and light absorption, and the unique advantages of this approach in the field of photocatalysis are substantiated by density functional theory. Under the synergistic effect of Cu4 clusters, the electronic state density distribution of the Ag single-atom catalyst substrate is drastically altered, which realizes the increase of substrate active sites and rapid charge separation and transfer. Compared with the pristine substrate g-C3N4, the new electronic state distribution and the generation of impurity energy levels lead to the narrowing of the band gap from 2.77 to 1.83 eV, accelerating the transfer and separation of electrons and holes, and enlarging the visible light absorption range from 410 to 760 nm, thus improving the solar energy utilization. Despite the reduced band gap, the conduction and valance band edges of (Ag, Cu4) codoped g-C3N4 still have sufficient potential to split water. Therefore, to improve the photocatalytic performance under visible light, simultaneous codoping of the Ag single atom and Cu4 cluster on g-C3N4 is an effective strategy. The study provides theoretical support for further optimization of single-atom catalysts.

Exploration of the structure, electronic and optical properties of AB 2(PO3)5 polyphosphates: a first-principle approach

The density functional theory method was applied using the gradient PBE, incorporating the hybrid PBE0 functional along with dispersion corrections D3(BJ). These objectives were accomplished through the utilization of the CRYSTAL package, employing a localized atomic orbital basis. Calculations encompassing crystal properties, including electronic, structural, and linear/nonlinear opto-electronic characteristics, were conducted for monoclinic AB 2(PO3)5. Specifically, the polyphosphates investigated in this study are RbPb2(PO3)5, CsPb2(PO3)5, KBa2(PO3)5, and RbBa2(PO3)5. It was demonstrated that in monoclinic phosphates, phosphorus and oxygen atoms form infinite chains [PO4]∞ based on the· ⋯ O1-P-O1 ⋯ ·structure. Alkali metal and lead (barium) atoms are surrounded by oxygen atoms O2, forming polyhedra. Infrared absorption spectra calculations confirmed the presence of chain backbone structural units. Additionally, band structure and partial density of electronic states were determined. The nature of valence and unoccupied states was also investigated. In lead-doped compounds, lead atoms contribute to the formation of upper-valence and lower-unoccupied states. Conversely, in barium-doped compounds, the upper valence states are primarily formed by O2 p-states, while the lower unoccupied states are formed by phosphorus. Also, the coefficients of second harmonic generation and birefringence were calculated, assessing the potential use of phosphates as nonlinear optical materials.

Exploration of structural, electrical, and thermoelectric properties of two-dimensional [formula omitted] in three phases through ab initio investigations

In this study, the structural, electrical, and thermoelectric properties for three phases of two-dimensional WTe2 have been investigated using first-principles study and semiclassic Boltzmann theory. The results of the electronic density of states have represented band gaps of 1.026, 1.021, and 1.048 eV for phase 1, phase 2, and phase 3, respectively. Furthermore, the largest value of the Seebeck coefficient at 300 K belonged to phase 2 with a value of 1585.21 μV/K at the chemical potential of 0.45 eV. In addition, the largest value of electrical conductivity per relaxation time was related to phase 1 at 300 K with the value of 3.42 × 1020Ω−1 m−1 s−1 at the chemical potential of -1.94 eV. Moreover, the largest value of the thermoelectric power factor per relaxation time occurred for phase 1 at 700 K with a value of 48.62 × 1016μW m−1 K−2 s−1 at the chemical potential of -1.17 eV.

Interaction of H2S with perfect and O-covered Pd(100) surface: A first-principles study

Using density functional theory (DFT) calculations, we investigated the dissociative mechanism of H2S adsorption and its dissociation on both clean and oxygen covered Pd (100) surface. For adsorption mechanism, the site preference was considered for H2S and HS monomers on both surfaces. The results suggest that H2S is energetically adsorbed on high symmetry sites, particularly the hollow site, on clean surface and top site on O-covered Pd (100) surface. Chemisorption of HS is stronger than H2S at the favorable hollow site on clean surface and O-covered surface. The energy barriers for S–H bond-breaking during the first H2S dehydrogenation are 0.35, 0.07, 0.32, and 0.16 eV, while for second dehydrogenation are 0.32 and 0.30 eV, respectively. On the oxygen-covered surface, the H2S adsorption site transitions from bridge to the top site and their energy barrier for first-order decomposition is 0.05 eV, significantly lesser than that observed on a clean surface. To examine more, the electronic densities of states as well as d-band center model were used to characterize the interaction of adsorbed H2S with the surfaces. Overall, our findings show that H2S decomposition on these surfaces is exothermic and relatively easy, but the presence of surface oxygen hinders the breaking process of H–S bond due to kinetic and thermodynamic factors.

Generation of femtosecond spin-polarized current pulses at Fe/MgO interface by quasi-static voltage

The generation of short spin-current pulses is essential for fast spintronic devices. So far, spin current pulses are generated by femtosecond laser pulses which drive spins from a ferromagnetic metal layer. However, the need for miniaturization, simplicity and energy efficiency favour electric-field control of spintronic devices over optic or thermal control. Here, we combine ab initio calculations of electronic density of states at MgO/Fe interface with continuous model for charge transport to investigate the dynamics of the spin-dependent potential. We demonstrate that the voltage-driven instability of the electronic band structure due to the electronic resonant states at the Fe/MgO interface results in the generation of the femtosecond spin-polarized current pulse with the spin polarization up to P=7 00 % that propagates from the interface to the bulk. The dynamics of the current pulses driven by the Stoner instability depends neither on the dielectric relaxation time nor on the details of how the instability is achieved by changing the voltage, i.e. as long as the voltage changes are slow (quasi-static) with respect to the time determined by the spin diffusion constant, being of the order of fs. The presence of the instability can be detected by THz time-domain spectroscopy or pump-probe techniques.

Unveiling the optoelectronic properties of bulk, monolayer, and bilayer TiS2: A DFT approach

Over the years, there has been significant research aimed at improving the performance of titanium disulfides (TiS2) in a wide range of applications, including lubricants, batteries, thermoelectric and electronic devices, catalysts, superconductors, photovoltaic devices, and more. This work investigates the optoelectronic properties of TiS2 using Density Functional Theory (DFT) calculations. The slab models were constructed for bulk, bilayer, and monolayer TiS2 (001) planes based on the 1T-TiS2 hexagonal phase. The GGA-PBE functional yielded the most accurate bandgaps: 0.178 eV (bulk), 0.047 eV (bilayer), and 0.112 eV (monolayer). The calculated lattice constants for bulk TiS2 with GGA-PBE were a = b = 3.407 Å and c = 5.697 Å, with an equilibrium volume of 57.24 ų. Electronic density of states (DOS) analysis revealed semiconducting behavior for both bulk and monolayer TiS2, with dominant peaks at the valence band. Bilayer TiS2 exhibited a higher DOS in the conduction band, indicating a more conductor-like character. Light absorption calculations showed the strongest peak for bilayer TiS2 (∼610,000 cm⁻¹ at 14.8 eV), followed by monolayer (∼13 eV) and bulk (∼12 eV). These results suggest that bulk TiS2 is preferable for applications requiring superior electrical properties, while bilayer TiS2 is more advantageous for applications focusing on light capture.

Ionic conduction and cathodic properties of CaMO3 (M=Fe and Mn) electrode materials via molecular dynamics and first-principles simulations

Calcium-ion(Ca-ion) batteries are gaining ever-increasing attention for next-generation energy storage systems due to affordability, highly abundant, high energy density, high theoretical capacity, and low redox potential close to Li-ion. In this work, we deployed the first-principles and classical molecular dynamics simulations to investigate the electronic and diffusive properties of isostructural ternary perovskite CaMO3 (M= Fe and Mn). The transport properties at various temperatures from ion dynamics and electronic properties of CaMO3 perovskites are examined using classical molecular dynamics and quantum mechanical simulations, respectively. We present the microscopic origin of the diffusion of multivalent ions like Ca2+ within the crystal structure of perovskite material and the effects of two transition metals, manganese and iron. Dynamic studies of Ca-ions were performed using molecular dynamic simulation, which depicts the diffusivity and conductivity of Ca-ion in CaMO3 material. We find that the diffusivity in both the crystals increases with temperature; as a result, conductivity increases. Among both the crystals, CaFeO3 requires less activation energy for diffusion and ionic conduction than CaMnO3. Using density functional theory, we calculated specific capacity, electronic density of states, phase stability and equilibrium cell voltage, and charge transfer process during intercalation-deintercalation from first-principles calculations. The electronic behavior of these materials shows that CaFeO3 has better electronic and transport properties than CaMnO3.

Evolution of ferromagnetism and electrical resistivity in Sb-doped Cr4PtGa17

We describe the doping effects on a metallic breathing pyrochlore compound, Cr4PtGa17. Upon doping with Sb, i.e., Cr4Pt(Ga1-xSbx)17, it was found that a selective doping on one of the seven Ga sites occurs. With increasing dopant level, the ferromagnetism in the parent compound is gradually suppressed, along with a decrease in fitted Curie-Weiss temperature (from 61 (1) K to −1.8 (1) K) and effective moment (from ∼2.26 μB/f.u. to ∼0.68 μB/f.u.). Low-temperature heat capacity measurements confirm the absence of magnetic ordering above 0.4 K for the three most doped samples. Meanwhile, electrical resistivity measurements display a metal-semiconductor transition with increasing Sb contents, which is attributed to an increase of Fermi energy based on the calculations of electronic band structure and density of states. Moreover, we have speculated that the ferromagnetism in Cr4PtGa17 is governed by itinerant electrons according to our observations. This study of Sb-doping effect on Cr4PtGa17 provides deeper understanding of magnetism of this system and possibilities for future modifications.

Strain-modulated intercalated phases of Pb monolayer with dual periodicity in SiC(0001)-graphene interface

Intercalation of metal atoms at the SiC(0001)-graphene (Gr) interface can provide confined 2D metal layers with interesting electronic properties. The intercalated Pb monolayer (ML) has shown the coexistence of the Gr(10 × 10)-moiré and a stripe phase, which still lacks understanding. Using density functional theory calculation and thermal annealing with ab initio molecular dynamics as motivated by experiment, we have studied the formation energy of Gr/Pb/SiC(0001) for different Pb coverages. Near the coverage of a Pb(111)-like ML mimicking the (10 × 10)-moiré, we find a slightly more stable stripe structure, where one half of the structure has compressive strain with Pb occupying the Si-top sites and the other half has tensile strain with Pb off the Si-top sites. This stripe structure along the Gr zigzag direction has a periodicity of 2.3 nm across the [1 2¯ 10] direction agreeing with the previous observations using scanning tunneling microscopy. Analysis with electron density difference and density of states show the tensile region has a more metallic character than the compressive region, while both are dominated by charge transfer from Pb ML to SiC(0001). The small energy difference between the stripe and Pb(111)-like structures means the two phases are almost degenerate and can coexist, which explains the experimental observations.

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.

Design, preparation and properties of biomedical Ti-Nb quaternary alloys with high strength and low modulus: insights from first-principles calculations

In this paper, we designed and developed biomedical β-type Ti-Nb quaternary alloy materials with high strength and low modulus. Building upon the d-electron alloy design method and the valence electron concentration e/a method, we use a Python program and thermodynamic theoretical parameters to determine a Ti-Nb quaternary alloy with the characteristics of a single-phase solid solution. Subsequently, we engage in theoretical and experimental investigations on the low modulus alloys identified through first-principles calculations. The results show that both Ti7Nb6Zr1Al2 and Ti11Nb2Ta2Al1 maintain a single β phase before and after cold rolling, which is related to the strong electronic density of states of s and p orbitals at low energy levels in the crystal structure of the two alloys. Ti11Nb2Ta2Al1 has a strong charge distribution on the (001) crystal plane, which causes a large amount of internal stress under large deformation conditions to promote grain crushing and weaken the intensity of the (001)[1-10] texture in the ODF diagram of 2 = 45°. The cold-rolled Ti11Nb2Ta2Al1 exhibits better corrosion resistance and biocompatibility than the cold-rolled Ti7Nb6Zr1Al2, and the good biocompatibility is related to the strong covalent bond between Al and Ta that inhibits the diffusion of Al ions. 90% cold-rolled Ti11Nb2Ta2Al1 stands out as an exceptionally promising orthopedic implant material due to its high elastic allowable strain (ReH/E), good corrosion resistance and biocompatibility.

Electrical resistivity and magnetic susceptibility of Al-Ni-Co-Cu-Zr high-entropy alloys in solid and liquid states

Electrical resistivity and magnetic susceptibility of Al-Ni-Co-Cu-Zr alloys with different component ratios are studied in a wide temperature range including both solid and liquid states. The abnormal behavior of properties is discovered in the temperature range 700–1200 K. The increase of magnetic atoms concentration (mainly cobalt) in the alloys composition leads to increase of properties anomalies. Some parameters of the electronic structure - paramagnetic Curie temperature, effective magnetic moment and density of electron states at Fermi level - are calculated from the experimental data.

Thermoelectric properties of InGaN/GaN superlattices structure with high indium composition quantum dots

High indium composition InGaN is a promising material for thermoelectric harvesting application, which can work at high temperature and extreme environments. Due to the strong composition segregation, high indium composition InGaN material usually forms localized quantum dots, which advantageously enhances the thermoelectric (TE) properties. In this research, the two-dimensional InGaN/GaN superlattices (SLs) structured TE material with high In composition of 35% quantum dots is first grown and characterized. Using open-circuit voltage measurement, the Seebeck coefficient (S) exhibits a high value of −571 μV/K. Analysis indicates this relatively high S value is related to the increased density of electron states near the Fermi level induced by the reduced dimensionality, resulting in a power factor of 11.83 × 10−4W/m·K2. The dense boundary between InGaN quantum dots also increases the interface phonon scattering, thereby suppressing the heat transportation and leading to a low thermal conductivity (k) value of 19.9 W/m·K. As a result, a TE figure of merit (ZT) value of 0.025 is demonstrated in the sample. This work first clarifies the impact of embedded quantum dots in InGaN/GaN SLs structure on TE properties. It is very conductive for the design and fabrication of low-dimensional GaN based TE device.

Unraveling pairon excitations and the antiferromagnetic contributions in the cuprate specific heat

Thermal measurements, such as entropy and specific heat, reveal key elementary excitations for understanding the cuprates. In this paper, we study the specific heat measurements on three different compounds La2−xSrxCuO4, Bi2Sr2CaCu2O8+δ and YBa2Cu3O7−δ and show that the data are compatible with ‘pairons’ and their excitations. However, the precise fits require the contribution of the antiferromagnetic entropy deduced from the magnetic susceptibility χ(T).Two temperature scales are involved in the excitations above the critical temperature Tc: the pseudogap T∗, related to pairon excitations, and the magnetic correlation temperature, Tmax, having very different dependencies on the carrier density (p). In agreement with our previous analysis of χ(T), the Tmax(p) line is not the signature of a gap in the electronic density of states, but is rather the temperature scale of strong local antiferromagnetic correlations which dominate for low carrier concentration. These correlations progressively evolve into paramagnetic fluctuations in the overdoped limit.Our results are in striking contradiction with the model of Tallon and Storey (2023), who reaffirm the idea of a T-independent gap Eg, whose temperature scale Tg=Eg/kB decreases linearly with p and vanishes at a critical value pc∼0.19.Finally, we discuss the unconventional fluctuation regime above Tc, which is associated with a mini-gap δ∼ 2meV in the pairon excitation spectrum. This energy scale is fundamental to the condensation mechanism.

Thermal insulation enhanced by the dopant-induced phonon softening discovered in thermoelectric Heusler compounds

Suppression of phonon transports is a key requirement to achieve high thermoelectric performance, which has been often realized by doping an element to enhance the phonon scattering. However, detailed origins behind the dopant-induced low lattice thermal conductivity (κph) have not yet been comprehensively understood. Here, we demonstrate a κph reduction mechanism induced by the phonon softening in the element-doped Fe2VAl thermoelectric Heusler compounds. Inelastic X-ray scattering experiments revealed that overall optical phonons are softened with increasing Ti-doping concentration in marked contrast to the Ta-doped Fe2VAl. By means of photoelectron spectroscopy, we found that the observed phonon softening is originating from the rigid-band shift of the electronic density of states and the consequent deviation of the pseudo-gap position from the Fermi level, which causes the energetic instability of the electronic system. This instability is accompanied by the reduction of the filled bonding states, giving rise to the phonon softening. This mechanism of κph reduction caused by the close correlation between electronic and phononic systems will shed new light on achieving low-κph and thereby developing unconventional high-performance thermoelectric materials.

Effect of thermal annealing on the average and local structure of superconducting polycrystalline NbRe films

Abstract NbxRe1−x is a non-centrosymmetric superconductor recently realized in thin film form. The access to the basic physics that governs this material is hindered by the polycrystalline structure of the films which consist of grains of small dimensions. In these conditions, films are not decisive in revealing the nature of the superconducting order parameter, and, in particular, the possible presence of a spin-triplet component. In this work, post-deposition annealing procedures were performed to improve the crystalline quality of the as-grown films. As determined by X-ray diffraction measurements, by tuning the annealing process, it was possible to increase the crystalline size from 1-2 nm up to several nanometers, beyond the values of the superconducting coherence length. Pair distribution function analyses revealed the non-centrosymmetric crystal structure of the treated NbRe films. Finally, electrical transport measurements, performed to study the relationship between structural and transport properties of the samples, showed an improved metallicity and a reduction of the superconducting critical temperature after the thermal treatment. This last result can be reasonably ascribed, for instance, to oxygen contamination, modification of the electronic density of states at the Fermi level, or change in the electron-phonon coupling. The results of this work are useful to realize films for future experiments meant to access nature of the superconducting order parameter.

Electronic structure of ultrathin single-walled platinum nanotubes

Using Density Functional Theory based on the plane wave method and linearized augmented cylindrical wave method, and taking into account the spin–orbit interaction, the structural, electronic and spin properties of ultrathin single-walled nanotubes consisting of six platinum rows are obtained. The nanotubes are found to possess metallic electronic mobility, including the nonchiral Pt(6,0) with the largest number (15G0) of ballistic channels. Analysis of the density of electronic states at Fermi level revealed that the chiral Pt(5,1) has a difference in concentration of mobile electrons with opposite spins of 1.42 times, and up to 3–4 times under a weak torsional strain.

Application of PLA/GO/ZnO and PLA/GO/Cu2O as sensor

Polylactic acid modified with graphene oxide (PLA/GO) is proposed to interact with ZnO through 6 different schemes. Density functional theory at B3LYP/LANL2DZ level was utilized to calculate total dipole moment (TDM), HOMO/LUMO energy gap (ΔE) and to map the molecular electrostatic potential (MESP). Results indicated that PLA/GO interacted with ZnO through O-atom forming PLA/GO/OZn composite. This composite interacts with methane, hydrogen sulfide, humidity (H2O), carbon dioxide and ethanol. The same gases were supposed to interact further with PLA/GO/Cu2O. Adsorption energy for the interaction between each composite and the proposed gases were calculated. Both PLA/GO/OZn and PLA/GO/Cu2O composites interacted favorably with H2O. Adsorption energy for interaction of other gases with studied structures are generally low compared to H2O. PLA/GO/OZn have adsorption energy slightly higher than that of PLA/GO/Cu2O. PLA/GO/OZn has higher TDM values than those of PLA/GO/Cu2O, indicating a more polar material. Conversely, PLA/GO/Cu2O exhibited larger ΔE values than those of PLA/GO/OZn. TDM and energy gap results for both studied structures indicated good sensing capabilities. Further insights come from analyzing the calculated density of states (DOS) and partial density of states (PDOS). PLA/GO/Cu2O exhibited high peak for copper in its DOS and PDOS spectra compared to zinc and oxygen in case of PLA/GO/OZn. This means a higher density of available electronic states associated with Cu.

Simulation of quantum states in solid-state ferromagnetic nanostructures

Purpose of the article. Identification and analysis of mathematical expressions for the energy spectrum of charge carriers in nano-sized magnetic films of nickel and Ni-Cu (substrate), as well as NiO-Ni-Cu (substrate) structures.Methods. In this work, based on basic quantum mechanical concepts and taking into account the boundary conditions for coupled quantum wells, expressions for the energy spectrum of electrons are obtained. The ferrimagnetic properties of nickel are taken into account through the effective mass value. The solution of nonlinear equations that determine discrete energy levels was achieved by numerical methods using the Mathcad mathematical package.Results. Transcendental expressions for the energies of free charge carriers in quantum wells of ferromagnetic nickel films are obtained, and the influence of the position of nickel on the copper substrate is shown. It has been shown that the use of a copper substrate leads to an increase in the density of energy levels in the nickel nanofilm. The influence of the oxide layer on single-electron states in nanofilms of nickel and its oxide is considered within the framework of the Anderson model. Based on the numerical solution of the transcendental equations obtained in the work, the influence of the ratio of the thicknesses of a ferromagnetic metal and its oxide on the energy levels of electrons localized in the oxide layer is shown.Conclusions. The formulas presented in the work for the energy spectrum take into account the energy relief of a complex quantum well, the dimensions of the film, surface oxide, and the significant effective mass in the region of the ferromagnetic film. It has been shown that an increase in the effective mass in magnetic heterostructures leads to an increase in the electron density of states. It was found that the density of electronic states in the region of surface nickel oxide is practically independent of the thickness of the nickel film. The results and conclusions of the work can be used for theoretical prediction of the physical properties of magnetic nanostructures, in particular spintronic elements.

A DFT Computational Study of Type-I Clathrates A8Sn46-x (A = Cs or NH4, x = 0 or 2).

Semiconducting clathrates have attracted considerable interest in the field of thermoelectric materials. We report here a computational study on the crystal structure, the enthalpy of formation, and the physical properties of the following type-I clathrates: (a) experimentally studied Cs8Sn44 and hypothetical Cs8Sn46 and (b) hypothetical (NH4)8Sn46-x (x = 0 or 2). The ab initio VASP calculations for the nominal stoichiometries include the geometry optimization of the initial structural models, enthalpies of formation, and the electronic and phonon density of states. Comparison of the chemical bonding of the structural models is performed via the electron localization function. The results show that the presence and distribution of defects in the Sn framework for both Cs8Sn46-x and (NH4)8Sn46-x systems significantly alters the formation energy and its electrical properties, ranging from metallic to semiconducting behavior. In particular, one defect per six-membered Sn ring in a 3D spiro-network is the thermodynamically preferred configuration that results in the Cs8Sn44 and (NH4)8Sn44 stoichiometries with narrow-band gap semiconducting behavior. Moreover, the rotation of the ammonium cation in the polyhedral cavities is an interesting feature that may promote the use of ammonium or other small molecular cations as guests in clathrates for thermoelectric applications; this is due to the decrease in the lattice thermal conductivity.