Search

This paper presents a feature-centric strategy for predicting adsorption energies of key CO2 reduction reaction (CO2RR) adsorbates, CO and H species, utilizing density functional theory-based calculations for eight adsorption sites and considering alloying effects of nine transition metals at single-atom concentrations. Here, we explore a class of materials consisting of a majority host metal where individual atoms of a different element are dispersed called single-atom alloys (SAA). A total of eight feature selection methods are assessed within Gradient Boosting Regression and Linear Regression models. This study proposes a practical and effective two-stage approach that narrows down the initial 86 features to subsets of 10 and 7 for CO and H adsorption energy predictions, respectively, with the arithmetic mean of valence electrons (VE-am) feature consistently emerging as highly influential, validated through permutation and Shapley additive explanations-based feature importance analyses. The models exhibit robust performance on unseen data, indicating their generalization capability. The findings emphasize VE-am as a potential key machine learning feature for CO2RR on SAA surfaces and underline the effectiveness of the feature-centric approach in understanding feature impacts in machine learning models for CO2RR on SAA systems. Additionally, while other features based on structural, electronic and elemental properties may not individually impact the model significantly, their collective contribution plays a vital role in achieving more accurate adsorption energy predictions. [ABSTRACT FROM AUTHOR]

Materials with versatile physical properties are essential for contemporary physical society, especially in electronics, renewable energy, transportation, medicine, and more. This intact capability holds the potential for a revolutionary shift towards environmentally friendly renewable energy sources. Consequently, the exploration of materials that encompass multiple functions becomes highly imperative. This study is concentrated on comprehending the physical characteristics of elastic and optoelectronic materials to propose novel, highly efficient materials suitable for photovoltaic device applications. Within this paper, the fundamental study of fluoroperovskite properties in the context of density functional theory is undertaken, employing the full potential linearized augmented plane wave approach. Specifically, fluoroperovskite ZnXF3 (X = Sr, Ba) is scrutinized concerning its structural, electronic, optical, and elastic attributes. The optimized crystal structural parameters for both compounds are determined as 4.41 Å for ZnSrF3 and 4.52 Å for ZnBaF3, employing the Birch-Murnaghan fitting approach for the unit cell energy versus unit cell volume. All fundamental physical properties are subsequently calculated using these optimized lattice constants. To address strongly correlated electron systems, the recently developed Modified Beck-Johnson potential is employed in this research. The tolerance factor "τ" is computed for both materials, yielding values of 0.98 for ZnSrF3 and 0.86 for ZnBaF3, affirming the structural stability of these perovskite crystal structures. The analysis of electronic properties reveals that both compounds exhibit a metallic behavior, for ZnXF3 (X = Sr, Ba) fluoroperovskites. Furthermore, the research explores the potential of these selected compounds by computing their optical properties within the energy range of 0–14 eV for incident photons, with a focus on potential optoelectronic applications. Additionally, mechanical properties for both materials are assessed using the IRelast package, with results indicating that ZnXF3 (X = Sr, Ba) fluoroPerovskites are mechanically stable, resistant to abrasion, ductile, and anisotropic. The precision and accuracy of the reported findings provide strong support for the potential applications of zinc-based ZnXF3 (X = Sr, Ba) fluoroperovskites in photovoltaic and modern semiconductor industries. [ABSTRACT FROM AUTHOR]

In the present work, we numerically and experimentally study the Co 3 - x Ni x O 4 (spinel-like oxides) system. Using the perturbative density functional theory (p-DFT) method, we start the study from the homogeneous sample ( x = 0 ), obtaining the main electronic properties (band structure (BS), density of states (DOS), and Fermi surface (FS)). Subsequently, we doped (x) with Ni atoms in different proportions (0–7% respectively, taking 56 atoms as 100% and the percentage of doping, on this percentage). As we increase the doping (x ≠ 0) , we have found that the forbidden gap decreases and the Fermi energy (FE) decreases, causing the material to exhibit a transition phase for a particular doping value. In addition, we find that more bands are generated when the system is doped, which would be responsible for the phase transition. The data from the theoretical analysis carried out in this paper was compared with the experimental data of various widely accepted works. Some of the results, when compared with the information available from the experimental ones, show good agreement. [ABSTRACT FROM AUTHOR]

Checkpoint kinases 1 and 2 (CHK1 and CHK2) are enzymes that are involved in the control of DNA damage. At the present time, these enzymes are some of the most important targets in the fight against cancer since their inhibition produces cytotoxic effects in carcinogenic cells. This paper proposes the use of spirostans (Sp), natural compounds, as possible inhibitors of the enzymes CHK1 and CHK2 from an in silico analysis of a database of 155 molecules (S5). Bioinformatics studies of molecular docking were able to discriminate between 13 possible CHK1 inhibitors, 13 CHK2 inhibitors and 1 dual inhibitor for both enzymes. The administration, distribution, metabolism, excretion and toxicity (ADMETx) studies allowed a prediction of the distribution and metabolism of the potential inhibitors in the body, as well as determining the excretion routes and the appropriate administration route. The best inhibition candidates were discriminated by comparing the enzyme-substrate interactions from 2D diagrams and molecular docking. Specific inhibition candidates were obtained, in addition to studying the dual inhibitor candidate and observing their stability in dynamic molecular studies. In addition, Highest Occupied Molecular Orbital—Lowest Unoccupied Molecular Orbital (HOMO-LUMO) interactions were analyzed to study the stability of interactions between the selected enzymes and spirostans resulting in the predominant gaps from HOMOCHKs to LUMOSp (Highest Occupied Molecular Orbital of CHKs—Lowest Unoccupied Molecular Orbital of spirostan). In brief, this study presents the selection inhibitors of CHK1 and CHK2 as a potential treatment for cancer using a combination of molecular docking and dynamics, ADMETx predictons, and HOMO-LUMO calculation for selection. [ABSTRACT FROM AUTHOR]

Hexagonal boron nitride is rapidly gaining interest as a platform for photonic quantum technologies, due to its two-dimensional nature and its ability to host defects deep within its large band gap that may act as room-temperature single-photon emitters. In this review paper we provide an overview of (1) the structure, properties, growth and transfer of hexagonal boron nitride; (2) the creationof colour centres in hexagonal boron nitride and assignment of defects by comparison with ab initio calculations for applications in photonic quantum technologies; and (3) heterostructure devices for the electrical tuning and charge control of colour centres that form the basis for photonic quantum technology devices. The aim of this review is to provide readers a summary of progress in both defect engineering and device fabrication in hexagonal boron nitride based photonic quantum technologies. [ABSTRACT FROM AUTHOR]

Context: The mechanisms for the formation of the first C − C bond and lower olefins on methanol to olefins (MTO) conversion on H-ZSM-5 had been focused in dispute. In this paper, density functional theory has been used to study the reaction mechanisms of methanol to olefins on ZSM-5. The configurations of reactants, intermediates, products and transition state of the numerous reactions involved in such a process have been optimized, as well as the elementary reactions related to these configurations were determined by the calculation of corresponding activation energy barriers and reaction heats. Here, two different kinds of the mechanisms were proposed for the formation of dimethyl ether (DME), one involving an associative interaction of two methanol molecules with the zeolite Brønsted acid sites and the other occurring via a surface methoxy species and a methanol molecule. A critical intermediate of the methoxy methyl cation was theoretically verified by the reaction of the methoxy species and dimethyl ether. Besides, it was found that the first intermediates containing a C − C bond were 1,2-dimethoxyethane and 2-methoxy-ethanolare, in which the former was formed from methoxy species with dimethyl ether and the latter was formed from methanol by onium ions((CH3)2O+CH2CH2OCH3), respectively. For the whole reaction mechanism, the results in this paper indicated that the ethene formation is more favorable than propylene formation due to the low activation energy barrier for ethene formation (123.49 vs. 162.09 kJ.mol−1). From these calculations, it would be concluded that ethene is the first alkene product that induces the occurrence of the hydrocarbon pool mechanism. Methods: All the periodic density function theory (DFT) calculations were performed by the Vienna Ab Initio Simulation package (VASP). The interaction between nucleus and valence electron was described using the pseudopotentials found in the projector augmented wave (PAW) method. PBE-D3 was used in the whole DFT calculations and CI-NEB was used to locate transition state. [ABSTRACT FROM AUTHOR]

Context and results : In this paper, the crystal structure, electronic, optical, and mechanical properties of SrVO3 have been systematically studied by first-principles calculation. The results show that the calculated lattice parameters are in good agreement with the experimental values of X-ray diffraction. The density of states is described in detail in this paper. By analyzing the crystal structure and electronic properties of SrVO3, the magnetic properties of SrVO3 are obtained from the one unpaired electrons of V and the exchange interaction between two V ions. At the same time, a detailed analysis of the optical properties of SrVO3 was conducted, and it was found that it is transparent in the visible light range. Finally, the mechanical properties of SrVO3 are calculated, which can provide some references for future research. Computational method: In this paper, a first-principles method based on density functional theory (DFT) is reported for PBE-GGA analysis using the plane wave-pseudo potential method in a quantum concentrate packet, U value of 7 eV to V-d and a U value of 2 eV to O-p, Grimme correction by DFT-D method. The k points in the Brillouin region are set to 4 × 4 × 4. The energy convergence criterion for self-consistent field calculation is set at 5.0 × 10−6 eV/atom, and the cutoff energy is 1170 eV. In this paper, the force acting on each atom is not more than 0.01 eV/Å, the maximum stress is not more than 0.02GPa, and the maximum atomic displacement is 5 × 10−4 Å. [ABSTRACT FROM AUTHOR]

Context and results : In this paper, the crystal structure, electronic, optical, and mechanical properties of SrVO3 have been systematically studied by first-principles calculation. The results show that the calculated lattice parameters are in good agreement with the experimental values of X-ray diffraction. The density of states is described in detail in this paper. By analyzing the crystal structure and electronic properties of SrVO3, the magnetic properties of SrVO3 are obtained from the one unpaired electrons of V and the exchange interaction between two V ions. At the same time, a detailed analysis of the optical properties of SrVO3 was conducted, and it was found that it is transparent in the visible light range. Finally, the mechanical properties of SrVO3 are calculated, which can provide some references for future research. Computational method: In this paper, a first-principles method based on density functional theory (DFT) is reported for PBE-GGA analysis using the plane wave-pseudo potential method in a quantum concentrate packet, U value of 7 eV to V-d and a U value of 2 eV to O-p, Grimme correction by DFT-D method. The k points in the Brillouin region are set to 4 × 4 × 4. The energy convergence criterion for self-consistent field calculation is set at 5.0 × 10−6 eV/atom, and the cutoff energy is 1170 eV. In this paper, the force acting on each atom is not more than 0.01 eV/Å, the maximum stress is not more than 0.02GPa, and the maximum atomic displacement is 5 × 10−4 Å. [ABSTRACT FROM AUTHOR]

The degradation of concrete and reinforced concrete structures is a significant technical and economic challenge, requiring continuous repair and rehabilitation throughout their service life. Geopolymers (GPs), known for their high mechanical strength, low shrinkage, and durability, are being increasingly considered as alternatives to traditional repair materials. However, there is currently a lack of understanding regarding the interface bond properties between new geopolymer layers and old concrete substrates. In this paper, using advanced computational techniques, including quantum mechanical calculations and stochastic modeling, we explored the adsorption behavior and interaction mechanism of aluminosilicate oligomers with different Si/Al ratios forming the geopolymer gel structure and calcium silicate hydrate as the substrate at the interface bond region. We analyzed the electron density distributions of the highest occupied and lowest unoccupied molecular orbitals, examined the reactivity indices based on electron density functional theory, performed Mulliken charge population analysis, and evaluated global reactivity descriptors for the considered oligomers. The results elucidate the mechanisms of local and global reactivity of the oligomers, the equilibrium low-energy configurations of the oligomer structures adsorbed on the surface of C-(A)-S-H(I) (100), and their adsorption energies. These findings contribute to a better understanding of the adhesion properties of geopolymers and their potential as effective repair materials. [ABSTRACT FROM AUTHOR]

Developing advanced hydrogen storage materials with high capacity and efficient reversibility is a crucial aspect for utilizing hydrogen source as a promising alternate to fossil fuels. In this paper, we have systematically investigated the hydrogen storage properties of neutral and negatively charged C9N4 monolayer based on density functional theory (DFT). Our foundings indicate that injecting additional electrons into the adsorbent significantly boosts the adsorption capacity of C9N4 monolayer to H2 molecules. The gravimetric density of negatively charged C9N4 monolayer can reach up to 10.80 wt% when fully covered with hydrogen. Unlike other hydrogen storage methods, the storage and release processes happen automatically upon introducing or removing extra electrons. Moreover, these operations can be easily adjusted through activating or deactivating the charging voltage. As a result, the method is easily reversible and has tunable kinetics without requiring particular activators. Significantly, C9N4 is proved to be a suitable candidate for efficient electron injection/release due to its well electrical conductivity. Our work can serve as a valuable guide in the quest for a novel category of materials for hydrogen storage with high capacity. [ABSTRACT FROM AUTHOR]

Copyright of Journal of Atomic & Molecular Physics (1000-0364) is the property of Journal of Atomic & Molecular Physics Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Copyright of Journal of Atomic & Molecular Physics (1000-0364) is the property of Journal of Atomic & Molecular Physics Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Gas sensors are essential devices to detect harmful gases that are present in the environment. Metal oxide semiconductors (MOSs) are used as sensing materials to detect harmful gases. Some of the metal oxides, like ZnO, SnO2, WO3, NiO, etc. have been used to detect the gases. This paper provides a theoretical study of gas sensing using MOSs. Many programs are available for the theoretical Density Functional Theory (DFT) approach. The theoretical calculation provides many properties about the sensing material, like electronic properties, magnetic properties, charge difference calculation, and Vander wall interaction between the sensing material surface and adsorbing molecule. The nanostructure provides better gas sensing performance due to its high surface-to-volume ratio. This paper is based on the DFT study and provides gas-sensing results using electronic properties. [ABSTRACT FROM AUTHOR]

In this paper, theoretical investigations of structural, elastic and thermal properties of Zn3P2 material were done using Quantum ESPRESSO code based on density functional theory. The generalized gradient approximation (GGA) exchange correlation-functional helped to model the atomic interaction. First, the structural optimization procedure was carried out, and hence, the optimized structural parameters were utilized to obtain six independent elastic constants C 1 1 , C 1 2 , C 1 3 , C 3 3 , C 4 4 , and C 6 6 for the Zn3P2 tetragonal structure. Accordingly, these elastic constants were used to determine the elastic moduli such as the Bulk modulus, Young's modulus, and shear modulus, as well as other mechanical parameters such as Pugh's ratio, Poisson's ratio, anisotropic ratio, sound velocities and Debye temperature. Calculations of thermodynamic properties such as vibrational energies, vibrational free energies, and fixed volume heat capacities, were performed within the implementation of the Thermo_pw code. Elastic calculations confirmed that this compound is characterized by mechanical stability at zero pressure and 0K temperature, ionic bonding, a high degree of anisotropy, and typical ductility. An observable increase in Debye vibrational energies, entropies and constant volume heat capacities of this compound with increasing temperature was detected throughout the thermodynamic calculations, unlike vibrational free energy which revealed a pronounced decrease as temperature increased. [ABSTRACT FROM AUTHOR]

This paper introduces the HEX (High-pressure Elemental Xstals) database, a complete database of the ground-state crystal structures of the first 57 elements of the periodic table, from H to La, at 0, 100, 200 and 300 GPa. HEX aims to provide a unified reference for high-pressure research, by compiling all available experimental information on elements at high pressure, and complementing it with the results of accurate evolutionary crystal structure prediction runs based on Density Functional Theory. Besides offering a much-needed reference, our work also serves as a benchmark of the accuracy of current ab-initio methods for crystal structure prediction. We find that, in 98% of the cases in which experimental information is available, ab-initio crystal structure prediction yields structures which either coincide or are degenerate in enthalpy to within 300 K with experimental ones. The main manuscript contains synthetic tables and figures, while the Crystallographic Information File (cif) for all structures can be downloaded from the related figshare online repository. [ABSTRACT FROM AUTHOR]

Surface enhanced Raman spectroscopy (SERS) is a powerful analytical technique that has found application in the trace detection of a wide range of contaminants. In this paper, we report on the fabrication of 2D silver nanodendrites, on silicon chips, synthesized by electrochemical reduction of AgNO3 at microelectrodes. The formation of nanodendrites is tentatively explained in terms of electromigration and diffusion of silver ions. Electrochemical characterization suggests that the nanodendrites do not stay electrically connected to the microelectrode. The substrates show SERS activity with an enhancement factor on the order of 106. Density functional theory simulations were carried out to investigate the suitability of the fabricated substrate for pesticide monitoring. These substrates can be functionalized with cyclodextrin macro molecules to help with the detection of molecules with low affinity with silver surfaces. A proof of concept is demonstrated with the detection of the herbicide 2-methyl-4-chlorophenoxyacetic acid (MCPA). [ABSTRACT FROM AUTHOR]

The infrared and laser Raman spectra of 4, 5-dimethyl-2-nitroaniline were measured and used for experimental spectrum analysis for current work. On a computational level, Hartree-Fock and density functional theory were employed to perform geometry and vibrational spectral analysis. Here, scaled frequencies are displayed in addition to IR, Raman intensities, and decreased masses. Utilizing HF/6-31+G (d, p), HF/6-311++G (d, p), and B3LYP/6-31+G (d, p) approaches, the various thermodynamical parameters are tabulated. These include entropy, enthalpy, and specific heat. The geometrical footprints, such as bond length and bond angles, are further explored in this paper on a computational level. [ABSTRACT FROM AUTHOR]

Baicalein (5,6,7-trihydroxyflavone: C15H10O5, a typical flavonoid), the predominated component of Scutellaria baicalensis Georgi (a traditional Chinese medicine, i.e., Huang Qin), has been simulating great interests due to its various promising and advantage. Numerous molecular properties can be theoretically investigated by quantum chemistry calculation based on the density functional theory, producing stable and reliable results comparable to the case through experimental method. In this work, we systematically studied the molecular properties of baicalein by performing the analyses (geometry, infrared spectrum, bond order, molecular orbital, density of states, localized molecular orbital, localized orbital locator, electron localization function, π-electron population, aromaticity, electrostatic potential, atomic charge, etc.) based on the theoretical quantum chemistry computation with the setup of B3LYP/def2-TZVP. No doubt, our work will provide assistance and theoretical guidance for further research on the component from the traditional Chinese medicine, such as the baicalein involved in this paper, in the future. [ABSTRACT FROM AUTHOR]

Inbuilt high energy band gap and resistivity cause harm to the intrinsic molybdenum trioxide (MoO3) for utilizing it directly in gas sensing and optoelectronic devices. Doping with transition metal ions can be an optimistic solution to these problems. By doping four side of modification of a material is possible. At first, doping can curtail the width of the energy band of semiconductor materials, thereby largely boosting the photo-sensitivity of the material and intensifying the light consumption that is more suitable for anti-laser devices and light source substances. The second is that doping can widen the material's band gap, which can significantly reduce the purities of the substance, improve absorbance, and make it suitable for strong interference semiconductor films and aperture materials. Third, changing the material's charge carrier density and effective mass can significantly improve conductivity. This is mostly relevant for conductive devices and photosensitive materials. Finally, changing the material's valance electron location influences the magnetic moment created by the spin of elementary particles in the entire system, allowing the magnetic characteristics of the substance to be regulated, which is especially useful for diluted magnetic semiconductor (DMS) materials. The investigation report of the structural, electrical, and optical characteristics of Cobalt (Co)-doped orthorhombic-phase MoO3 utilizing plane-wave pseudo-potential technique based on first-principles computation is presented in this paper. The computation has been executed using density a functional theory (DFT)-based CASTEP computer program with the generalized gradient approximation (GGA) together with the Perdue-Burke-Ernzerhof (PBE) exchange–correlation function. Acquired structural parameters present good consistency with the former reported experimental data. The resultant electronic band structure reveals that pure MoO3 shows an indirect energy band gap of 1.873 eV/2.312 eV whereas Co doping causes band narrowing of about 0.94 eV/1.36 eV with PBE/HSE techniques. The total and partial density of states (PDOS) have been studied comparatively, for pure and Co-doped MoO3, respectively. The absorption coefficient, loss function, reflectivity, refractive index, extinction coefficient, dielectric function, along with optical conductivity have also been determined to analyze the optical properties of Co-doped MoO3. Co-doped MoO3 offers higher conductivity while decreasing resistivity, compared to the undoped case. The present study ensures that Co-doped α- MoO3 can be competently employed as a functional material in gas sensing and optoelectronic devices. [ABSTRACT FROM AUTHOR]

Optimization problems on probability measures in ℝ d are considered where the cost functional involves multi-marginal optimal transport. In a model of N interacting particles, for example in Density Functional Theory, the interaction cost is repulsive and described by a two-point function c ⁢ (x , y) = ℓ ⁢ (| x - y |) where ℓ : ℝ + → [ 0 , ∞ ] is decreasing to zero at infinity. Due to a possible loss of mass at infinity, non-existence may occur and relaxing the initial problem over sub-probabilities becomes necessary. In this paper, we characterize the relaxed functional generalizing the results of [4] and present a duality method which allows to compute the Γ-limit as N → ∞ under very general assumptions on the cost ℓ ⁢ (r) . We show that this limit coincides with the convex hull of the so-called direct energy. Then we study the limit optimization problem when a continuous external potential is applied. Conditions are given with explicit examples under which minimizers are probabilities or have a mass < 1 . In a last part, we study the case of a small range interaction ℓ N ⁢ (r) = ℓ ⁢ (r / ε) ( ε ≪ 1 ) and we show how the duality approach can also be used to determine the limit energy as ε → 0 of a very large number N ε of particles. [ABSTRACT FROM AUTHOR]

The contents of alkali and alkaline earth metals are higher in Zhundong coal, and there are serious problems of slagging and fouling during the combustion process. Therefore, it is of great significance to reveal the mechanism of slagging and fouling in the boiler of Zhundong coal. In this paper, first-principle calculations based on density functional theory are used to study the competition mechanism of alkaline metal oxides during the combustion process in Zhundong coal by establishing the Na2O(110)/CaO(100)-SiO2(100) double-layer interface model. The results show that the bond lengths of the surface of Na2O(110) and CaO(100) with SiO2(100) after adsorption were generally lengthened and the value of bond population became smaller, which formed a stable binding energy during the reaction. The electron loss of Na is 0.05 e, the electron loss of Ca is 0.03 e, and the electron loss of Na2O is greater than that of CaO. The charge transfer on the surface of Na2O with SiO2 is obviously higher than that of CaO and the orbital hybridization on the surface of CaO with SiO2 is weaker than that on the surfaces of Na2O with SiO2. Na2O is easier to react with SiO2 than CaO. The adsorption energies on the surface of Na2O and CaO with SiO2 are −5.56 eV and −0.72 eV, respectively. The adsorption energy of Na2O is higher than that of CaO, indicating that Na2O is more prone to adsorption reactions and formation of Na-containing minerals and other minerals, resulting in more serious slagging. In addition, the XRD analyses at different temperatures showed that Na-containing compounds appeared before Ca-containing ones, and the reaction activity of Na2O is stronger than that of CaO in the reaction process. The experimental results have good agreement with the calculation results. This provides strong evidence to reveal the slagging and fouling of Zhundong coal. [ABSTRACT FROM AUTHOR]

Incorporating metal cations into V2O5 has been proven to be an effective method for solving the poor long-term cycling performance of vanadium-based oxides as electrodes for mono- or multivalent aqueous rechargeable batteries. This is due to the existence of a bilayer structure with a large interlayer space in the V2O5 electrode and to the fact that the intercalated ions act as pillars to support the layered structure and facilitate the diffusion of charged carriers. However, a fundamental understanding of the mechanical stability of multi-ion-co-intercalated bilayered V2O5 is still lacking. In this paper, a variety of pillared vanadium pentoxides with two types of co-intercalated ions were studied. The root-mean-square deviation of the V-O bonds and the elastic constants calculated by density functional theory were used as references to evaluate the stability of the intercalated compounds. The d-band center and electronic band structures are also discussed. Our theoretical results show that the structural characteristics and stability of the system are quite strongly influenced by the intercalating strategy. [ABSTRACT FROM AUTHOR]

In this paper we report on a computationally cost-effective method designed to estimate the thermal conductivity of optical materials based on cubic oxide including mixed ones, i.e. solid solutions of different oxides. The proposed methodology take advantage from Density Functional Theory (DFT) calculations to extract essential structural parameters and elastic constants which represent the inputs for revised versions of Slack and Klemens equations relating thermal conductivity to elastic constants. Slack equation is modified by the introduction of a corrective factor that incorporates the Grüneisen parameter γ, while in the revised Klemens equation a distortion parameter d accounting for the impact of point defects on lattice symmetry is added, which is a critical factor in determining thermal conductivity in optical materials with mixed compositions. The theoretical results were found in good agreement with experimental data, showing the reliability of our proposed methodology. [ABSTRACT FROM AUTHOR]

This paper systematically investigates the structure, stability, and electronic properties of niobium carbide clusters, NbmCn (m = 5, 6; n = 1–7), using density functional theory. Nb5C2 and Nb5C6 possess higher dissociation energies and second-order difference energies, indicating that they have higher thermodynamic stability. Moreover, ab initio molecular dynamics (AIMD) simulations are used to demonstrate the thermal stability of these structures. The analysis of the density of states indicates that the molecular orbitals of NbmCn (m = 5, 6; n = 1–7) are primarily contributed by niobium atoms, with carbon atoms having a smaller contribution. The composition of the frontier molecular orbitals reveals that niobium atoms contribute approximately 73.1% to 99.8% to NbmCn clusters, while carbon atoms contribute about 0.2% to 26.9%. [ABSTRACT FROM AUTHOR]

Deep eutectic solvents (DESs) are now enjoying an increased scientific interest due to their interesting properties and growing range of possible applications. Computational methods are at the forefront of deciphering their structure and dynamics. Type IV DESs, composed of metal chloride and a hydrogen bond donor, are among the less studied systems when it comes to their understanding at a molecular level. An important example of such systems is the zinc chloride–urea DES, already used in chemical synthesis, among others. In this paper, the ZnCl2(urea)2 crystal is studied from the point of view of its structure, infrared spectrum, and intermolecular interactions using periodic density functional theory and non-covalent interactions analysis. The two main structural motifs found in the crystal are a strongly hydrogen-bonded urea dimer assisted by chloride anions and a tetrahedral Zn(II) coordination complex. The crystal is composed of two interlocking parallel planes connected via the zinc cations. The infrared spectrum and bond lengths suggest a partially covalent character of the Zn−Cl bonds. The present analysis has far-reaching implications for the liquid ZnCl2–urea DES, explaining its fluidity, expected microstructure, and low conductivity, among others. [ABSTRACT FROM AUTHOR]

The superadiabatic dynamical density functional theory (superadiabatic-DDFT) is a promising new method for the study of colloidal systems out-of-equilibrium. Within this approach, the viscous forces arising from interparticle interactions are accounted for in a natural way by explicitly treating the dynamics of the two-body correlations. For bulk systems subject to spatially homogeneous shear, we use the superadiabatic-DDFT framework to calculate the steady-state pair distribution function and the corresponding viscosity for low values of the shear-rate. We then consider a variant of the central approximation underlying this superadiabatic theory and obtain an inhomogeneous generalization of a rheological bulk theory due to Russel and Gast. This paper thus establishes for the first time a connection between DDFT approaches, formulated to treat inhomogeneous systems, and existing work addressing nonequilibrium microstructure and rheology in bulk colloidal suspensions. [ABSTRACT FROM AUTHOR]

In this paper, benchmark results are presented on the calculation of vertical electronic excitation energies using a long-range second-order polarization propagator approximation (SOPPA) description with a short-range density functional theory description based on the Perdew–Burke–Ernzerhof (PBE) functional. The excitation energies are investigated for 132 singlet states and 71 triplet states across 28 medium-sized organic molecules. The results show that overall SOPPA-srPBE always performs better than PBE and that SOPPA-srPBE performs better than SOPPA for singlet states, but slightly worse than SOPPA for triplet states when CC3 results are the reference values. [ABSTRACT FROM AUTHOR]

Since the 1940s, it has been known that diffusion in crystalline solids occurs due to lattice defects. The diffusion of defects can have a great impact on the processing and heat treatment of materials as the microstructural changes caused by diffusion can influence the material qualities and properties. It is, therefore, vital to be able to control the diffusion. This implies that we need a deep understanding of the interactions between impurities, matrix atoms, and intrinsic defects. The role of density functional theory (DFT) calculations in solid-state diffusion studies has become considerable. The main parameters to obtain in defect diffusion studies with DFT are formation energies, binding energies, and migration barriers. In particular, the utilization of the nudged elastic band and the dimer methods has improved the accuracy of these parameters. In systematic diffusion studies, the combination of experimentally obtained results and theoretical predictions can reveal information about the atomic diffusion processes. The combination of the theoretical predictions and the experimental results gives a unique opportunity to compare parameters found from the different methods and gain knowledge about atomic migration. In this Perspective paper, we present case studies on defect diffusion in wide bandgap semiconductors. The case studies cover examples from the three diffusion models: free diffusion, trap-limited diffusion, and reaction diffusion. We focus on the role of DFT in these studies combined with results obtained with the experimental techniques secondary ion mass spectrometry and deep-level transient spectroscopy combined with diffusion simulations. [ABSTRACT FROM AUTHOR]

Introducing defects into Pd-based metallene has been shown to significantly enhance its electrocatalytic performance. In this study, we embedded a new type of atomic-scale cavities into the basal plane of PdMo bimetallene (c-PdMo) through precise etching. These cavities introduced tensile strain and increased the generalized coordination number (CN ̅), resulting in superior performance in formate oxidation reaction (FOR) and methanol oxidation reaction (MOR), with mass activities of 5.01 mA μ g NM − 1 and 5.38 mA μ g NM − 1 , respectively. Notably, a two-electrode system comprising commercial Pt/C and c-PdMo coated on carbon paper achieved cell voltages of only 0.517 V and 0.362 V at 10 mA cm−2 for FOR and MOR, respectively. Additionally, density functional theory calculations revealed that the deliberate lattice tensile strain and enhanced coordination numbers reduced the D-band center of defective PdMo, which improved OH adsorption and reduced CO adsorption, thus optimizing FOR and MOR catalysis on the surface of c-PdMo bimetallene. [Display omitted] • PdMo bimetallene with atomic-scale cavities (c-PdMo) was prepared via etching. • Atomic-scale cavities can regulate coordination number and strain of bimetallene. • Atomic-scale cavities can modulate the surface adsorption energies of CO and OH. • c-PdMo exhibited highly-efficient mass activity for FOR and MOR. [ABSTRACT FROM AUTHOR]

Plasmon polaritons, or plasmons, are coupled oscillations of electrons and electromagnetic fields that can confine the latter into deeply subwavelength scales, enabling novel polaritonic devices. While plasmons have been extensively studied in normal metals or semimetals, they remain largely unexplored in correlated materials. In this paper, we report infrared (IR) nano-imaging of thin flakes of CsV3Sb5, a prototypical layered Kagome metal. We observe propagating plasmon waves in real-space with wavelengths tunable by the flake thickness. From their frequency-momentum dispersion, we infer the out-of-plane dielectric function ϵ c that is generally difficult to obtain in conventional far-field optics, and elucidate signatures of electronic correlations when compared to density functional theory (DFT). We propose correlation effects might have switched the real part of ϵ c from negative to positive values over a wide range of middle-IR frequencies, transforming the surface plasmons into hyperbolic bulk plasmons, and have dramatically suppressed their dissipation. Plasmons polaritons, or collective excitations of electrons and electromagnetic fields, have been rarely studied in layered correlated materials. Shiravi et al. report hyperbolic plasmon polaritons in thin flakes of the Kagome metal CsV3Sb5 and discuss correlation effects on their formation and tunability. [ABSTRACT FROM AUTHOR]

The synergistic effect between metals is of great significance for improving the performance of materials, but the mechanism of synergistic catalytic of bimetallic has rarely been reported in the hydrolysis of sodium borohydride (NaBH 4 , SB). In this paper, a flower shaped Co 2 FeO 4 catalyst with high catalytic performance was selected from a series of Co x M 3-x O 4 (M = Fe, Ni, Cu) catalysts by controlling the composition. Based on the results of XPS characterization and density functional theory (DFT) calculation, the influence of component control on catalytic performance was discussed and explained from the perspective of electronic structure, and the "valence band center" and "D-band center" descriptors were introduced into the SB hydrolysis reaction. The simulation analysis results showed that the synergistic effect between Co–Fe elements resulted in the smallest center shift of the D band, the smallest binding energy of the hydrolysis reaction, and the best promoting effect on the electronic structure, manifested as the best catalytic performance. The calculation results were consistent with the XPS characterization results and the experimental results of hydrolysis performance testing, revealing the principle of bimetallic synergistic effect on catalytic performance. The synergistic effect between metals is of great significance for improving the performance of materials, but the mechanism of synergistic catalytic of bimetallic has rarely been reported in the hydrolysis of sodium borohydride (NaBH 4 , SB). In this paper, a flower shaped Co 2 FeO 4 catalyst with high catalytic performance was selected from a series of Co x M 3-x O 4 (M = Fe, Ni, Cu) catalysts by controlling the composition. Based on the results of XPS characterization and density functional theory (DFT) calculation, the influence of component control on catalytic performance was discussed and explained from the perspective of electronic structure, and the "valence band center" and "D-band center" descriptors were introduced into the SB hydrolysis reaction. The simulation analysis results showed that the synergistic effect between Co–Fe elements resulted in the smallest center shift of the D band, the smallest binding energy of the hydrolysis reaction, and the best promoting effect on the electronic structure, manifested as the best catalytic performance. The calculation results were consistent with the XPS characterization results and the experimental results of hydrolysis performance testing, revealing the principle of bimetallic synergistic effect on catalytic performance. [Display omitted] • Flower-like Co 2 FeO 4 showed the best catalytic performance. • The "D-band center" and "valence -band center" of Co 2 MO 4 were studied. • Composition and electronic control improve the catalytic performance of Co 2 MO 4. • The adsorption configuration of H 2 O on the Co 2 MO 4 (311) surface was studied. [ABSTRACT FROM AUTHOR]

A molecule–electrode interface with different coupling strengths is one of the greatest challenges in fabricating reliable molecular switches. In this paper, the effects of bridging manner on the transport behaviors of a dimethyldihydropyrene/cyclophanediene (DHP/CPD) molecule connected to two graphene nanoribbon (GNR) electrodes have been investigated by using the non-equilibrium Green's function combined with density functional theory. The results show that both current values and ON/OFF ratios can be modulated to more than three orders of magnitude by changing bridging manner. Bias-dependent transmission spectra and molecule-projected self-consistent Hamiltonians are used to illustrate the conductance and switching feature. Furthermore, we demonstrate that the bridging manner modulates the electron transport by changing the energy level alignment between the molecule and the GNR electrodes. This work highlights the ability to achieve distinct conductance and switching performance in single-molecular junctions by varying bridging manners between DHP/CPD molecules and GNR electrodes, thus offering practical insights for designing molecular switches. [ABSTRACT FROM AUTHOR]

Compared with traditional water electrolysis, electrolysis of seawater has larger resources and a brighter future. However, seawater contains more elements that have greater corrosive effects on electrodes; especially chloride ions (seawater contains more chloride ions) have the greatest impact. The existence of the corrosion problem creates greater difficulties in electrolyzing seawater, further limiting the efficiency of the electrocatalyst for electrolysis of seawater. In this paper, we report a Mn-doped Ni 2 P/Cu 3 P as an environmentally friendly monofunctional electrode for seawater electrolysis, which was made by a simple hydrothermal phosphatization operation method. The experimental results show that Mn-doped Ni 2 P/Cu 3 P presents overpotential of only 161 mV for oxygen evolution reaction (OER) at iR compensation of 90 and a current density of 10 mA cm−2. It has a small Tafel slope (25.15 mV dec−1) and a large capacitance (9.58 mF cm−2 on 1 × 1 nickel foam), which exceeds most reported oxygen evolution activities of non-precious metal-based electrocatalysts for electrolysis of alkaline seawater. The performance of Ni 2 P/Cu 3 P was probably significantly enhanced due to Mn doping by some characterization means. Through Density functional theory (DFT) analysis, it is known that the doping of Mn gives a large enhancement in the adsorption energy of water when Ni 2 P/Cu 3 P is electrolyzed with seawater. This paper provides train of thought for the exploration of excellent electrocatalysts for electrolysis of alkaline seawater. The experimental results show that Mn-dopedNi 2 P/Cu 3 P present overpotential of only 161 mV at i-R compensation of 90 for oxygen evolution reaction in alkaline seawater. [Display omitted] • Mn-doped Ni 2 P/Cu 3 P electrodes was synthesized for the first time through hydrothermal processes. • The overpotential of Mn-doped Ni 2 P/Cu 3 P electrode is only 161 mV at 10 mA cm−2 for OER. • The doping of Mn gives a large enhancement in the adsorption energy of water. [ABSTRACT FROM AUTHOR]

The development of efficient non-noble metal electrocatalysts for the oxygen evolution reaction (OER) under acidic conditions remains a critical challenge. Herein, we report a N-doped carbonaceous component-engineered Co3O4 (NCEC) catalyst synthesized via the sol-gel method. Dopamine hydrochloride (DA)-derived nitrogen-doped carbonaceous components were found to boost the OER performance of Co3O4. The optimized catalyst can reach an overpotential as low as 330 mV in 1 M H2SO4 at a current density of 10 mA cm-2 and maintains a good long-term stability of 60 hours. In particular, we found that the thermodynamic overpotential was inversely proportional to the content of oxidized N and pyridinic N, whereas it was directly proportional to the pyrrolic-N content. Our experiments and density functional theory (DFT) calculations confirm that the optimized catalyst exhibits enhanced charge transfer and the oxidized N species on Co3O4 is responsible for the high catalytic activity. Our study suggests that the performance of NCEC in acidic media can be further optimized by enhancing the content of oxidized N species. [ABSTRACT FROM AUTHOR]

Copyright of Industrial Water Treatment is the property of CNOOC Tianjin Chemical Research & Design Institute and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Based on the first principle, this paper uses the generalised gradient approximation density functional theory and slab model to investigate the dissociation of methane (CH4→CH3 + H) on the surfaces of Co group (Co, Rh, Ir) and Ni group (Ni, Pd, Pt), and investigate the influence of PtIr(100), PdRh(100) and PtPd(100) on methane decomposition. From the calculated activation energies of methane dissociation on single metal surfaces and alloy surfaces,we find that Pt and Ir are better catalysts for methane dissociation in the single metals studied. In addition, methane dissociation (CH4→CH3 + H) on PtIr(100) and PdRh(100) surfaces are easier than that on single metal surfaces(Co, Rh, Ir, Ni, Pd, Pt). [ABSTRACT FROM AUTHOR]

In this paper, the adsorption behaviours of the MeOH-DMC azeotropic system onto α-Al2O3 were investigated from both practical and theoretical aspects for the first time. The experimental results showed that the static MeOH- and DMC-adsorption capacities of α-Al2O3 were 325.52 and 70.32 mg·g−1, respectively. The selectivity S was 4.63 and the dynamic separation factor α was 4.2. Then, density functional theory (DFT) was used to reveal possible interactions between the constructed azeotrope clusters and the α-Al2O3 (0 0 1) surface. Molecular simulation results indicated that although there were different azeotropic clusters in the bulk liquid, most of the H-bonds were destroyed when they approached the solid surface. The MeOH dimers were adsorbed onto both Al and O sites via chemisorption and H-bonds, while DMC monomers mainly occupied the Al sites. Thus, chemisorption on Al sites and multi-layer adsorption played a critical role in selective adsorption. Moreover, the competition between MeOH and DMC for adsorption sites might also cause a big difference between the MeOH- and DMC-adsorption capacities of α-Al2O3. [ABSTRACT FROM AUTHOR]

The two-dimensional electrochemical Y2C's low work function and strong charge transfer qualities limit its applicability in catalysis due to its poor catalytic activity. In this paper, based on density functional theory calculations, we use two techniques to increase the HER catalytic activity of the Y2C monolayer: substitution doping (XC) and adsorption doping (XT) of non-metal (X = N, P, O, S, and F). The results showed that the absolute values of hydrogen free energies (ΔGH*) of the substitutional dopants of PC, SC and adsorptive dopants of NT, OT, ST, and PT had increased catalytic activity compared with those of the pristine Y2C monolayer (−0.673 eV). It was highlighted that the adsorption doping of PT can further reduce the adsorption free energy of the pristine Y2C monolayer to −0.19 eV, which is close to the optimal zero value, and the binding energy of the hydrogen atoms on the Y2C surface significantly increased from −0.913 to −0.438 eV, which is more favorable for the desorption of hydrogen atoms. These results demonstrate that the doping of non-metals activates the adsorption of hydrogen atoms on monolayer Y2C and provides a feasible method for hydrogen generation. [ABSTRACT FROM AUTHOR]

Copyright of Journal of Atomic & Molecular Physics (1000-0364) is the property of Journal of Atomic & Molecular Physics Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

The research on the anti-CO poisoning performance of Pt catalyst for direct methanol fuel cell (DMFC) has been the focus of scientists. Nafion membrane is one of the indispensable components in DMFC. In this paper, the effect of Nafion on the anti-CO poisoning of Pt catalyst was studied by density functional theory (DFT). It is found that under the action of Nafion, the adsorption energy of CO on Pt(111) catalyst increases by about 5 eV (the grater the adsorption energy, the better the CO poisoning resistance), which greatly increases the CO poisoning resistance of Pt catalyst. By further calculation, the better the adsorption performance of Nafion on Pt(111) surface, the stronger the anti-CO poisoning ability of Pt catalyst. [ABSTRACT FROM AUTHOR]

In this paper, the importance of isospin symmetry and its breaking in elucidating the properties of atomic nuclei is reviewed. The quark mass splitting and the electromagnetic origin of the isospin symmetry breaking (ISB) for the nuclear many-body problem is discussed. The experimental data on isobaric analogue states cannot be described only with the Coulomb interaction, and ISB terms in the nucleon–nucleon interaction are needed to discern the observed properties. In the present work, the ISB terms are explicitly considered in nuclear energy density functional and spherical shell model approaches, and a detailed investigation of the analogue states and other properties of nuclei is performed. It is observed that isospin mixing is largest for the N = Z system in the density functional approach [ABSTRACT FROM AUTHOR]

Copyright of Journal of Synthetic Crystals is the property of Journal of Synthetic Crystals Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

In this paper, a detailed mechanism is discussed for two processes: deNOx and deN2O. An FAU catalyst was used for the reaction with Cu-Fe bimetallic adsorbates represented by a dimer with bridged oxygen. Partial hydration of the metal centres in the dimer was considered. Ab initio calculations based on the density functional theory were used. The electron parameters of the structures obtained were also analysed. Visualisation of the orbitals of selected structures and their interpretations are presented. The presented research allowed a closer look at the mechanisms of processes that are very common in the automotive and chemical industries. Based on theoretical modelling, it was possible to propose the most efficient catalyst that could find potential application in industry–this is the FAU catalyst with a Cu-O-Fe bimetallic dimer with a hydrated copper centre. The essential result of our research is the improvement in the energetics of the reaction mechanism by the presence of an OH group, which will influence the way NO and NH3 molecules react with each other in the deNOx process depending on the industrial conditions of the process. Our theoretical results suggest also how to proceed with the dosage of NO and N2O during the industrial process to increase the desired reaction effect. [ABSTRACT FROM AUTHOR]

The vast compositional and configurational spaces of multi-element metal halide perovskites (MHPs) result in significant challenges when designing MHPs with promising stability and optoelectronic properties. In this paper, we propose a framework for the design of B-site-alloyed ABX3 MHPs by combining density functional theory (DFT) and machine learning (ML). We performed generalized gradient approximation with Perdew–Burke–Ernzerhof functional for solids (PBEsol) on 3,159 B-site-alloyed perovskite structures using a compositional step of 1/4. Crystal graph convolution neural networks (CGCNNs) were trained on the 3159 DFT datasets to predict the decomposition energy, bandgap, and types of bandgaps. The trained CGCNN models were used to explore the compositional and configurational spaces of 41,400 B-site-alloyed ABX3 MHPs with a compositional step of 1/16, by accessing all possible configurations for each composition. The electronic band structures of the selected compounds were calculated using the hybrid functional (PBE0). Then, we calculated the optical absorption spectra and spectroscopic limited maximum efficiency of the selected compounds. Based on the DFT/ML-combined screening, 10 promising compounds with optimal bandgaps were selected, and from among these 10 compounds, CsGe0.3125Sn0.6875I3 and CsGe0.0625Pb0.3125Sn0.625Br3 were suggested as photon absorbers for single-junction and tandem solar cells, respectively. The design framework presented herein is a good starting point for the design of mixed MHPs for optoelectronic applications. [ABSTRACT FROM AUTHOR]

Context: In this paper, the optimum coverage of 4.44% and the optimum adsorption sites were determined for the Be3N2 adsorption system of O atoms at different coverages based on density functional theory. The electronic and optical properties of the model were investigated by applying bending deformation to the model at these coverage and adsorption sites. Adsorption of O atoms disrupts the geometrical symmetry of Be3N2, resulting in orbital rehybridization and lowering its band gap. Bending deformation causes the band gap of the adsorbed O atom structure of Be3N2 to first increase and then decrease, resulting in the modulation of its band gap. With increasing bending deformation, the adsorbed system is redshifts, and the degree of redshift increases with increasing bending deformation. Methods: All calculations in this paper were performed using the first-principles-based CASTEP module of Materials Studio (MS). The generalized gradient approximation (GGA) plane-wave pseudopotential method and the Perdew-Burke-Ernzerhof (PBE) Perdew et al. Phys Rev Lett 77:3865, 1996 generalized functional were used in the geometry optimization and calculation process to calculate the exchange–correlation potential between electrons. The effect of coverage on the electronic and optical properties of the Be3N2-adsorbed O atom system was investigated by adsorbing different numbers of O atoms on a monolayer of Be3N2. The Be3N2 protocell contains two N atoms and three Be atoms with a space community of P6/MMM (No.191). The original cell was expanded 3 times along the direction of the base vectors a and b in the Be3N2 plane to create a 3 × 3 × 1 monolayer Be3N2 supercell system. A vacuum layer of 15 Å is set in the direction of the crystal plane of the vertical monolayer Be3N2 supercell to eliminate interactions between adjacent layers. In the overall energy convergence test of the Be3N2 supercell, the plane wave truncation energy was set to 500 eV, and the energy difference between the calculations given in the literature Reyes-Serrato et al. J Phys Chem Solids 59:743-6, 1998 using 550 eV was less than 0.01 eV, verifying the reliability of the data at a truncation energy of 500 eV. The Monkhorst–Pack special k-point sampling method Monkhorst et al. Phys Rev B 13:5188, 1976 was used in the structural calculations, and the grid was set to 3 × 3 × 1. The geometric optimization parameters are set as follows: the self-consistent field iteration convergence criterion is 2.0 × 10−6 eV, and the iterative accuracy convergence value is not less than 1.0 × 10−5 eV/atom for the total force of each atom and less than 0.03 eV/Å for all atomic forces. In addition the high-symmetry k-point path is taken as Γ(0,0,0) → M(0,0.5,0) → K(− 1/3,2/3,0) → Γ(0,0,0) Chen et al, AIP Adv 8:105105, 2018. [ABSTRACT FROM AUTHOR]

Copyright of Journal of South China Agricultural University is the property of Gai Kan Bian Wei Hui and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

CuS is an encouraging photoelectrode candidate that meets the essential requirements for efficient solar‐to‐hydrogen production, but it has not been thoroughly studied. A CuS light absorber layer is grown by the self‐assembly of copper and sulfur precursors on a carbon paper (CP) electrode. Simultaneously, rGO is introduced as a buffer layer to control the optical and electrical properties of the absorber. The well‐ordered microstructural arrangement suppresses the recombination loss of electrons and holes owing to enhanced charge‐carrier generation, separation, and transport. The potential reaching 10 mA cm−2 in 1.0 m KOH solution is significantly lowered to 0.87 V, and the photocurrent density at 1.23 V is 94.7 mA cm−2. The computational result reveals that the potential‐determining step is sensitive to O* stability; the lower stability of O* in the thin layer of CuS/rGO decreases the free‐energy gap between the initial and final states of the potential‐determining step, resulting in a lowering of the onset potential. The faradaic efficiency for the photoelectrochemical oxygen evolution reaction in the optimized 2CuS/1rGO/CP photoanode is 98.60%, and the applied bias photon‐to‐current and the solar‐to‐hydrogen efficiencies are 11.2% and 15.7%, respectively, and its ultra‐high performance is maintained for 250 h. These record‐breaking achievement indices may be a trigger for establishing a green hydrogen economy. [ABSTRACT FROM AUTHOR]