Search

The recent discovery of MoB2 with a superconducting transition temperature (Tc) of up to 32 K at 100 GPa provides new insights into the metallization and subsequently high-Tc superconductivity of diborides, highlighting the potential of transition metals in these compounds. We herein re-evaluated the structure, mechanical, and superconducting properties of IrB4 under pressure up to 300 GPa using first-principles. Our calculations reveal that a new P21/c phase exhibiting a hardness of 15.75 GPa surpasses the stability of the C2/m structure identified through the particle swarm optimization at ambient pressure. Upon compressing, the P21/c phase transforms into an MgB2-type structure with a space group of P63/mmc at 62.5 GPa and then into the orthorhombic Cmca phase above 109 GPa. Unlike semiconductor behavior of the atmospheric pressure phase, the two high-pressure structures are metallic and superconducting, with Tc values of 29.90 for P63/mmc at 62.5 GPa and 13.45 K for Cmca at 125 GPa. Analysis of the electronic structure and electron–phonon coupling (EPC) reveals that the high Tc, similar to MgB2-type MoB2, stems from the Van Hove Singularities (VHS) near the Fermi level donated by transition metal Ir. The effect further enhances the EPC based on the boron contribution. More interestingly, pressure has little impacts on the position of the VHS. These findings provide a new platform for designing advanced high-Tc superconductors. [ABSTRACT FROM AUTHOR]

The recent discovery of MoB2 with a superconducting transition temperature (Tc) of up to 32 K at 100 GPa provides new insights into the metallization and subsequently high-Tc superconductivity of diborides, highlighting the potential of transition metals in these compounds. We herein re-evaluated the structure, mechanical, and superconducting properties of IrB4 under pressure up to 300 GPa using first-principles. Our calculations reveal that a new P21/c phase exhibiting a hardness of 15.75 GPa surpasses the stability of the C2/m structure identified through the particle swarm optimization at ambient pressure. Upon compressing, the P21/c phase transforms into an MgB2-type structure with a space group of P63/mmc at 62.5 GPa and then into the orthorhombic Cmca phase above 109 GPa. Unlike semiconductor behavior of the atmospheric pressure phase, the two high-pressure structures are metallic and superconducting, with Tc values of 29.90 for P63/mmc at 62.5 GPa and 13.45 K for Cmca at 125 GPa. Analysis of the electronic structure and electron–phonon coupling (EPC) reveals that the high Tc, similar to MgB2-type MoB2, stems from the Van Hove Singularities (VHS) near the Fermi level donated by transition metal Ir. The effect further enhances the EPC based on the boron contribution. More interestingly, pressure has little impacts on the position of the VHS. These findings provide a new platform for designing advanced high-Tc superconductors. [ABSTRACT FROM AUTHOR]

The recent development of accurate and efficient semilocal density functionals on the third rung of Jacob's ladder of density functional theory, such as the revised regularized strongly constrained and appropriately normed (r2SCAN) density functional, could enable rapid and highly reliable prediction of the elasticity and temperature dependence of thermophysical parameters of refractory elements and their intermetallic compounds using the quasi-harmonic approximation (QHA). Here, we present a comparative evaluation of equilibrium cell volumes, cohesive energy, mechanical moduli, and thermophysical properties (Debye temperature and thermal expansion coefficient) for 22 transition metals using semilocal density functionals, including the local density approximation (LDA), Perdew–Burke–Ernzerhof (PBE) and PBEsol generalized gradient approximations (GGAs), and the r2SCAN meta-GGA. PBEsol and r2SCAN deliver the same level of accuracies for structural, mechanical, and thermophysical properties. PBE and r2SCAN perform better than LDA and PBEsol for calculating cohesive energies of transition metals. Among the tested density functionals, r2SCAN provides an overall well-balanced performance for reliably computing cell volumes, cohesive energies, mechanical properties, and thermophysical properties of various 3d, 4d, and 5d transition metals using QHA. Therefore, we recommend that r2SCAN could be employed as a workhorse method to evaluate thermophysical properties of transition metal compounds and alloys in high throughput workflows. [ABSTRACT FROM AUTHOR]

Recent experimental advances in ultrafast science have put different processes occurring on the electronic timescale below a few femtoseconds in focus. In the present theoretical work, we demonstrate how the transformation and propagation of the density matrix in the basis of irreducible spherical tensors can be conveniently used to study sub-few fs spin–flip dynamics in core-excited transition metal compounds. With the help of the Wigner–Eckart theorem, such a transformation separates the essential dynamical information from the geometric factors governed by the angular momentum algebra. We show that an additional reduction can be performed by the physically motivated truncation of the spherical tensor basis. In particular, depending on the degree of coherence, the ultrafast dynamics can be considered semi-quantitative in the notably reduced spherical basis when only the total populations of the basis states of the given spin are of interest. Such truncation should be especially beneficial when the number of high-spin basis states is vast, as it reduces computational costs. [ABSTRACT FROM AUTHOR]

Recently, Kohn–Sham (KS) methods with new correlation functionals, called σ-functionals, have been introduced. Technically, σ-functionals are closely related to the well-known random phase approximation (RPA); formally, σ-functionals are rooted in perturbation theory along the adiabatic connection. If employed in a post-self-consistent field manner in a Gaussian basis set framework, then, σ-functional methods are computationally very efficient. Moreover, for main group chemistry, σ-functionals are highly accurate and can compete with high-level wave-function methods. For reaction and transition state energies, e.g., chemical accuracy of 1 kcal/mol is reached. Here, we show how to calculate first derivatives of the total energy with respect to nuclear coordinates for methods using σ-functionals and then carry out geometry optimizations for test sets of main group molecules, transition metal compounds, and non-covalently bonded systems. For main group molecules, we additionally calculate vibrational frequencies. σ-Functional methods are found to yield very accurate geometries and vibrational frequencies for main group molecules superior not only to those from conventional KS methods but also to those from RPA methods. For geometries of transition metal compounds, not surprisingly, best geometries are found for RPA methods, while σ-functional methods yield somewhat less good results. This is attributed to the fact that in the optimization of σ-functionals, transition metal compounds could not be represented well due to the lack of reliable reference data. For non-covalently bonded systems, σ-functionals yield geometries of the same quality as the RPA or as conventional KS schemes combined with dispersion corrections. [ABSTRACT FROM AUTHOR]

We explore new transition metal (TM) compound sub-nanoclusters, TM8X6 (TM = Mn, Fe, Co and X = P, B, As), using density functional theory. Their optimized geometric structures show the same polyhedral structure (tetrahexahedron) independent of a kind of TM and metalloid (X), where eight TM atoms form a cubic structure capped with six metalloid (X) atoms. Incorporating an extra TM atom into the TM cubic results in an endohedral structure, TM9X6. Encapsulation of an additional TM atom merely changes the binding energy except for the Co boride cluster. The binding energy of Co8B6 increases by incorporating an additional Co atom, in which it is observed that the electron density is accumulated between B and all Co atoms (Co atoms both at the center and at the edges), but in other clusters, the electron excess is found mainly between TM atoms. The MnnP6 (n = 8 and 9) clusters have a high adiabatic electron affinity (>6 eV) due to the relatively large difference in electronegativity between Mn and P. The highest occupied molecular orbital and lowest unoccupied molecular orbital gaps of all clusters lie in the visible range. The interaction between nanoclusters and graphene with a single vacancy is studied as a function of the different cluster landing site on the graphene, where the geometric structure change of the clusters strongly depends on the adsorption site. [ABSTRACT FROM AUTHOR]

There are diverse reactions including spin-state crossing, especially the reactions catalyzed by transition metal compounds. To figure out the mechanisms of such reactions, the discussion of minimum energy intersystem crossing (MEISC) points cannot be avoided. These points may be the bottleneck of the reaction or inversely accelerate the reactions by providing a better pathway. It is of great importance to reveal their role in the reactions by computationally locating the position of the MEISC points together with the reaction pathway. However, providing a proper initial guess for the structure of the MEISC point is not as easy as that of the transition state. In this work, we extended the nudged elastic band (NEB) method for multiple spin systems, which is named the multiple spin-state NEB method, and it is successfully applied to find the MEISC points while optimizing the reaction pathway. For more precisely locating the MEISC point, a revised approach was adopted. Meanwhile, our examples also suggest that special attention should be paid to the criterion to define an image optimized as the MEISC point. [ABSTRACT FROM AUTHOR]

Analytic energy gradients with respect to nuclear coordinates are derived and implemented for the self-consistent direct random phase approximation (sc-dRPA) method. In contrast to the more common non-self-consistent dRPA methods, the sc-dRPA method does not require a choice for the approach to generate the Kohn–Sham orbitals and eigenvalues serving as input for the dRPA correlation functional. The fact that the sc-dRPA total energy is variational facilitates the calculation of analytic gradients. The analytic gradients are tested against numerical ones and then used to calculate equilibrium geometries and vibrational frequencies for various molecules including weakly bonded dimers and transition metal compounds. The sc-dRPA method can compete in accuracy with Møller–Plesset perturbation theory of second order and with conventional density-functional methods within the generalized gradient approximation or of hybrid type. Indeed, sc-dRPA geometries and vibrational frequencies are most accurate in many cases. Moreover, the sc-dRPA method is robust in the sense that it is applicable to all considered molecules, whereas conventional density-functional methods are not applicable to dispersion bonded dimers, and Møller–Plesset perturbation theory of second order erroneously predicts a number of molecules to be unbound and yields completely wrong vibrational frequencies in some cases. The coupled cluster singles doubles methods yield geometries and vibrational frequencies of a quality that is inferior to that of the other considered methods. [ABSTRACT FROM AUTHOR]

Core–hole spectroscopies such as x-ray photoelectron spectroscopy (XPS) and high-resolution electron energy loss spectroscopy (HR-EELS) in combination with multiplet calculation are important tools to elucidate the electronic structure of transition metal compounds. This work presents a comparison between the electronic structure obtained by XPS and HR-EELS for polycrystalline perovskite-type Ba0.9Ca0.1Ti0.9Zr0.1O3. Raman analysis suggests that Ca2+ cations could partly occupy the Ti4+ cations in the B-site of a perovskite structure with the tetragonal phase. A multiplet structure was determined by XPS for Ti 2p and by HR-EELS for Ca L2,3 and Ti L2,3 edges. Octahedral (Oh) symmetry in the crystal field (CF) effects reproduces the local distortion of TiO6 octahedra. The charge transfer (CT) effects were also considered to reproduce L3-edge EELS shoulders and the satellite in the Ti 2p XPS region. CF and CT parameters, 10 Dq, (charge transfer energy) Δ, and (Coulomb repulsion energy) Udd, are reported for future reference. The broadening of the Ti L2-edge suggests the presence of the Coster–Kronig electron decay process. Multiplet calculation in Oh symmetry for the Ca L2,3-edge could support the Raman interpretation. [ABSTRACT FROM AUTHOR]

There are three essential problems in computational relativistic chemistry: Electrons moving at relativistic speeds, close lying states, and dynamical correlation. Currently available quantum-chemical methods are capable of solving systems with one or two of these issues. However, there is a significant class of molecules in which all the three effects are present. These are the heavier transition metal compounds, lanthanides, and actinides with open d or f shells. For such systems, sufficiently accurate numerical methods are not available, which hinders the application of theoretical chemistry in this field. In this paper, we combine two numerical methods in order to address this challenging class of molecules. These are the relativistic versions of coupled cluster methods and the density matrix renormalization group (DMRG) method. To the best of our knowledge, this is the first relativistic implementation of the coupled cluster method externally corrected by DMRG. The method brings a significant reduction of computational costs as we demonstrate on the system of TlH, AsH, and SbH. [ABSTRACT FROM AUTHOR]

Determining the multi-reference character of a molecular system and its impact on the limits within which its properties may be calculated accurately by different quantum chemical methods remains a difficult yet important task in computational chemistry. Especially, transition metal compounds continue to frequently provide a challenge to quantum chemists in this regard. In this work, we construct, analyze, and evaluate different computational protocols to determine the impact of the multi-reference character of transition metal compounds on their bond dissociation energies using a set of reference data for 60 diatomic molecules. We find that the fractional orbital density approach allows to determine two global indicators on a physically sound basis. These can subsequently be used to classify the assessed set of molecules with high accuracy into categories of systems for which their multi-reference character matters substantially for their bond dissociation energies and for which it does not. A comparison with earlier suggested thresholds for classification of molecular systems due to their multi-reference character suggests that our approaches yield substantially better performance. [ABSTRACT FROM AUTHOR]

In this study, the all-d-metal Heusler compounds Ni2MnT (T = Sc, Ti, V, Cr, Y, Zr, Nb, Mo, Hf, Ta, and W) were considered as representative examples, and the magnetism-dependent martensitic phase transition was systematically investigated by first-principles calculations. Comparative analysis of the calculated magnetic states-dependent elastic parameters, electronic structures, and thermodynamic parameters indicates that weakly magnetic Ni2MnT compounds with late transition metal atoms show higher possibilities of martensitic phase transition. Although magnetism is not the necessary condition for martensitic phase transition, the strong magnetic moment in Ni2MnT compounds with early transition metal atoms can suppress the occurrence of martensitic phase transition. When the magnetism is absent or becomes weak, the suppressed martensitic phase transition can be re-evoked. The current study indicates that magnetism plays an important role in determining the martensitic phase transition in all-d-metal Heusler compounds Ni2MnT. Careful control of the magnetism can serve as another parameter to tune martensitic phase transition in Ni−Mn-based all-d-metal Heusler compounds. This study can be helpful to explore and design outstanding candidate materials for solid-state refrigeration applications based on the martensitic phase transition. [ABSTRACT FROM AUTHOR]

While In3Rh has been predicted to be a three-dimensional Dirac semimetal, experimental studies of its physical properties are lacking. Here, we report the angular-dependent magnetoresistance (MR) measurements of In3Rh single crystals under high magnetic fields up to 32 T. The crystals show large, non-saturating linear MR, and remarkable quantum oscillations with multi-frequencies. Analysis of the quantum oscillations reveals that there are three bands hosting a nontrivial Berry phase, which is corroborated by first-principles calculations. Our work may provide a platform for exploring topological materials in indium-rich transition metal compounds. [ABSTRACT FROM AUTHOR]

Hubbard corrected density functional theory (DFT) methods, such as the DFT+U approach in Dudarev's approximation, are widely used for the description of energetics and electronic structure of strongly correlated materials, providing higher level of accuracy than local DFT calculations (e.g., local density approximation or generalized gradient approximation). However, the DFT+U method in Dudarev's formulation limits the introduced corrections to interactions between the electrons within the same spin channel, whereas interactions between the electrons with opposite spins are still treated using local DFT functional (e.g., Perdew-Burke-Ernzerhof). In recent years, the need for correction of these interactions between the electrons with opposite spins has been recognized and additional terms have been added to the Hubbard term to reflect it. Although such extended DFT+U functionals have been proposed, the form of respective Hamiltonian operator, defined as a total energy derivative over density with appropriate treatment of double counting corrections due to additional Hubbard terms, has not been explicitly presented. In this work, we provide an expression for such a type of Hamiltonian, which contains the respective double counting correction contributions. This formulation also allows evaluation of atomic forces, using computational settings discussed herein. In addition, we also introduce adjustments for too narrow theoretical bandgaps, using scissor operator technique. This allows for a greater level of corrections of energetics and magnetic properties of studied transition metal compounds, avoiding possible unphysical overlap between occupied and unoccupied electronic bands. [ABSTRACT FROM AUTHOR]

In the recently developed correlation factor (CF) model [Precechtelova et al., J. Chem. Phys. 143, 144102 (2015)], the exchange-correlation (XC) hole is approximated. Since various constraints satisfied by the XC-hole are known, approximations to it can be designed which largely avoid empirical adjustments. In the CF approach, the XC-hole is written as a product of an exchange hole times a CF. An important constraint satisfied by the CF model is that it correctly reproduces the exact exchange energy in the high density limit. This is achieved by employing the exact exchange-energy per particle ( ϵ X r ) as an input variable, i.e., the CF model builds on exact exchange. Variations of the initial CF model are proposed which ensure that the exact answer is obtained in the homogeneous limit. Furthermore, we apply a correction to the depth of the XC-hole that is designed to capture strong correlation. EC functionals that build on exact exchange, such as hybrids, often fail for systems that exhibit sizeable electron correlation. Despite this fact and despite the reduction of empiricism to a single parameter within CF, accurate atomization energies are obtained for strongly-correlated transition metal compounds. The CF model significantly improves upon widely used functionals such as Perdew-Burke-Ernzerhof (PBE), PBE hybrid, and Tao-Perdew-Staroverov-Scuseria (TPSS). [ABSTRACT FROM AUTHOR]

Topological superconductors have shown great potential in the search for unique quasiparticles such as Majorana fermions. Combining nontrivial band topology and superconductivity can lead to topological superconductivity due to the proximity effect. In this work, we used first principles calculations to predict that rock-salt phases of VC and CrC are superconducting with topologically nontrivial states. The phonon dispersions of these transition metal carbides displayed no imaginary frequencies, which suggests dynamic stability. Additionally, the presence of soft acoustic phonon bands supports the existence of Bardeen-Cooper-Schrieffer superconductivity in rock-salt VC and CrC. Therefore, these transition metal carbides are practical candidates for studying topological superconductors and their associated Majorana bound states. [ABSTRACT FROM AUTHOR]

The quantum size effect is a well-known fundamental scientific phenomenon. Due to quantum confinement, downscaling a system to small sizes should increase the bandgap of a solid state material. However, in this work, we present an exception: monolayers of nickel hydroxide have smaller bandgaps than their bulk analogues, due to the surface states appearing at energies within the bandgap region. Our findings are obtained by several state-of-the-art first principles calculations. [ABSTRACT FROM AUTHOR]

MAX phases are layered carbides or nitrides with the general formula Mn+1AXn, which exhibit a unique combination of ceramic- and metal-like properties. The effect of stacking a number (determined by n) remains to be elucidated and a priori is not clear whether, for a given chemistry, n significantly changes the intrinsic deformation behavior of these systems. In this work, we have studied the intrinsic deformation behavior of Tin+1AlCn and Tan+1AlCn (n = 1 … 5) using DFT-based calculations. Surprisingly, the results suggest that the stacking number tends to have a minimal effect on the intrinsic mechanical behavior of the systems studied. [ABSTRACT FROM AUTHOR]

Landau levels (LLs) are modified by the Fröhlich interaction which we investigate within the improved Wigner-Brillouin theory for energies both below and above the longitudinal-optical-continuum in monolayer MoS2, WS2, MoSe2, and WSe2. Polaron corrections to the LLs are enhanced in monolayer MoS2 as compared to WS2. A series of levels are found at ℏ ω L O + l ℏ ω c , and in addition, the Fröhlich interaction lifts the degeneracy between the levels n ℏ ω c and ℏ ω L O + l ℏ ω c resulting in an anticrossing. The screening effect due to the environment plays an important role in the polaron energy corrections, which are also affected by the effective thickness reff parameter. The polaron anticrossing energy gap Egap decreases with increasing effective thickness reff. [ABSTRACT FROM AUTHOR]

The structural, electronic, and magnetic properties of FeGen-/0 (n = 3-12) clusters were investigated by using anion photoelectron spectroscopy in combination with density functional theory calculations. For both anionic and neutral FeGen (n = 3-12) clusters with n ≤ 7, the dominant structures are exohedral. The FeGe8 -/0 clusters have half-encapsulated boat-shaped structures, and the opening of the boat-shaped structure is gradually covered by the additional Ge atoms to form Gen cage from n = 9 to 11. The structures of FeGe10 -/0 can be viewed as two Ge atoms symmetrically capping the opening of the boat-shaped structure of FeGe8, and those of FeGe12 -/0 are distorted hexagonal prisms with the Fe atom at the center. Natural population analysis shows that there is an electron transfer from the Ge atoms to the Fe atom at n = 8-12. The total magnetic moment of FeGen -/0 and local magnetic moment of the Fe atom have not been quenched. [ABSTRACT FROM AUTHOR]

In the present work, we use a machine learning method to construct a high-dimensional potential for tungsten disulfide using a charge equilibration neural-network technique. A training set of stoichiometric WS2 clusters is prepared in the framework of density functional theory. After training the neural-network potential, the reliability and transferability of the potential are verified by performing a crystal structure search on bulk phases of WS2 and by plotting energy-area curves of two different monolayers. Then, we use the potential to investigate various triangular nano-clusters and nanotubes of WS2. In the case of nano-structures, we argue that 2H atomic configurations with sulfur rich edges are thermodynamically more stable than the other investigated configurations.We also studied a number of WS2 nanotubes which revealed that 1T tubes with armchair chirality exhibit lower bending stiffness. [ABSTRACT FROM AUTHOR]

High accuracy electronic structure computations for small transition metal-containing molecules have been a long term challenge. Due to coupling between electronic and nuclear wave functions, even experimental/theoretical identification of the ground electronic state requires tremendous efforts. Quartic force fields (QFFs) are effective ab initio tools for obtaining reliable anharmonic spectroscopic properties. However, the method that employs complete basis set limit extrapolation ("C"), consideration of core electron correlation ("cC"), and inclusion of scalar relativity ("R") to produce the energy points on the QFF, the composite CcCR methodology, has not yet been utilized to study inorganic spectroscopy. This work takes the CcCR methodology and adapts it to test whether such an approach is conducive for the closed-shell, copper-containing molecules CuCN, CuOH, and CuCCH. Gas phase rovibrational data are provided for all three species in their ground electronic states. Equilibrium geometries and many higher-order rovibrational properties show good agreement with earlier studies. However, there are notable differences, especially in computation of fundamental vibrational frequencies. Even with further additive corrections for the inner core electron correlation and coupled cluster with full single, double, and triple substitutions (CCSDT), the differences are still larger than expected indicating that more work should follow for predicting rovibrational properties of transition metal molecules. [ABSTRACT FROM AUTHOR]

Creation and characterization of mixed valence states in transition-metal oxides are a fundamental approach to search for the unprecedented electronic and magnetic properties. In contrast to complex oxides, mixed-valence simple oxides tend to form binary or ternary phases, and turning a valence from one to next must be accompanied by structural transformations owing to a lower tolerance for oxygen non-stoichiometry. In this paper, epitaxial growth and transport properties of low-valence titanate thin films are reported to shed light on recently discovered superconducting γ-phase Ti3O5 (γ-Ti3O5). Single-phase TiO and Ti2O3 films and eutectic films including TiO, Ti2O3, and γ-Ti3O5 phases were independently grown on α-Al2O3 (0001) substrates by using pulsed-laser deposition. The X-ray diffraction measurements revealed clear epitaxial relationships with substrates and among three eutectic phases. Temperature dependence of the resistivity revealed that the γ-Ti3O5-rich films exhibited superconductivity with a maximum of transition temperature (TC) of 6.3 K. Distinct effects of the phase fraction on TC are found between TiO- and Ti2O3-enriched samples, suggesting the complex mechanisms of the superconducting proximity effect. [ABSTRACT FROM AUTHOR]

CoCrFeMnNi is a prototype fcc-structured high-entropy alloy. Numerous efforts have been paid to strengthen CoCrFeMnNi, by replacing Mn with other elements for an enhancement of the solid solution strengthening. 4d transition metals, including Zr, Nb, and Mo, are of interest for this purpose, since they have much larger atomic radii than that of Mn. However, Nb and Mo are known to have a low solid solubility in fcc-structured CoCrFeNi. Compared to Nb and Mo, Zr has an even larger atomic radius. The solid solubility of Zr in fcc-structured CoCrFeNi was investigated in this work, combining both experimental studies and thermodynamic calculations. In addition, based on previous results and new results obtained here, methods to predict the solid solubility in CoCrFeNiMx (M=Zr, Nb, and Mo) alloys were developed. Particularly, the average d-orbital energy level, Md, was re-evaluated in the present work, for an improved predictability of the solid solubility in fcc-structured high entropy alloys containing 4d transition metals. [ABSTRACT FROM AUTHOR]

Few compounds feature ice-shaping properties. Zirconium acetate is one of the very few inorganic compounds reported so far to have ice-shaping properties similar to that of ice-shaping proteins, encountered in many organisms living at low temperature. When a zirconium acetate solution is frozen, oriented and perfectly hexagonal ice crystals can be formed and their growth follows the temperature gradient. To shed light on the water/ice phase transition while freezing zirconium acetate solution, we carried out differential scanning calorimetry measurements. From our results, we estimate how many water molecules do not freeze because of their interaction with Zr cations. We estimate the colligative properties of the Zr acetate on the apparent critical temperature. We further show that the phase transition is unaffected by the nature of the base which is used to adjust the pH. Our results provide thus new hints on the ice-shaping mechanism of zirconium acetate. [ABSTRACT FROM AUTHOR]

La2Mo2O9 (LMO) thin films have been deposited on Pt/Ti/SiO2/Si substrates by pulsed laser deposition and the resistive switching (RS) characteristics of the Au/LMO/Pt devices has been investigated. The Au/LMO/Pt devices show excellent unipolar RS characteristics with high resistance ratio between high resistance state and low resistance state (LRS), good endurance, and retention performances. The results of temperature dependence of resistance and x-ray photoelectron spectroscopy suggest that the observed RS characteristics can be explained by the formation and rupture of conducting filaments composed of oxygen vacancies. Furthermore, the plot of the reset current (IR) as a function of the third harmonic coefficient (B0) caused by Joule heating during the reset process shows scaling behavior with a power law of IR∝ B0-δ. The IR and reset power (PR) can also be scaled to the resistance in LRS (R0), i.e., IR(PR) ∝ R0-α(β). The observed scaling behaviors indicate the importance of the Joule heating for the RS characteristics of Au/LMO/Pt devices. These results demonstrate the potential application of LMO thin film in a nonvolatile memory device. [ABSTRACT FROM AUTHOR]

Layered transition metal dichalcogenides are emerging as key materials in nanoelectronics and energy applications. Predictive models to understand their growth, thermomechanical properties, and interaction with metals are needed in order to accelerate their incorporation into commercial products. Interatomic potentials enable large-scale atomistic simulations connecting first principle methods and devices. We present a ReaxFF reactive force field to describe molybdenum ditelluride and its interactions with copper. We optimized the force field parameters to describe the energetics, atomic charges, and mechanical properties of (i) layered MoTe2, Mo, and Cu in various phases, (ii) the intercalation of Cu atoms and small clusters within the van derWaals gap of MoTe2, and (iii) bond dissociation curves. The training set consists of an extensive set of first principles calculations computed using density functional theory (DFT).We validate the force field via the prediction of the adhesion of a single layer MoTe2 on a Cu(111) surface and find good agreement with DFT results not used in the training set. We characterized the mobility of the Cu ions intercalated into MoTe2 under the presence of an external electric field via finite temperature molecular dynamics simulations. The results show a significant increase in drift velocity for electric fields of approximately 0.4 V/Å and that mobility increases with Cu ion concentration. [ABSTRACT FROM AUTHOR]

Recently, two-dimensional transition metal dichalcogenides have intrigued much attention due to their promising applications in optoelectronics. The electrostatic property investigation of WSe2 nanostructures is essential for device application. Here, the interlayer screening effects of WSe2 nano-plates with different thicknesses were investigated by measuring surface potential employing Kelvin probe force microscopy. Simultaneously, charges can be injected into WSe2 nanoplate by means of conducting atomic force microscopy to tune the electrostatic properties of WSe2 nanostructures. Our experimental results have some important implications for improving performance of WSe2-based optoelectronic devices through interface or surface engineering. [ABSTRACT FROM AUTHOR]

Ilmenite structure is a good playground to explore magnetism in honeycomb lattices owing to the existence of an intriguing variety of magnetism in 3d transition metal compounds. Because of the absence of magnetic ions, ilmenite-type MgTiO3 is a promising candidate for d0 transparent insulators to reveal general features of TiO6 honeycomb layers. In this study, we found an optimum growth condition to synthesize ilmenite-type single-crystalline MgTiO3 thin films on Al2O3(0001) substrates by pulsed-laser deposition. By increasing oxygen pressure from roughly 10−6 to 10−1 Torr, we obtained (0001)-oriented MgTiO3 thin films with suppression of segregation of a Mg2TiO4 phase. On the triangular lattice of Al2O3, twin-domain formation is suppressed with decreasing deposition rate, resulting in the synthesis of single-crystalline MgTiO3 thin films. The bandgap of the MgTiO3 film was evaluated to be about 4.4 eV by optical absorption spectra, which implies d0 transparent insulator. [ABSTRACT FROM AUTHOR]

The rapid development of lithium ion batteries (LIBs) and sodium ion batteries (SIBs) requires novel anode materials with high performance. Phase engineering has been regarded as a promising strategy used for enhancing the electrochemical performance of LIBs and SIBs due to its superiority of selectively synthesizing the phases with favorable electrochemical performance and reasonably designing the electrode materials with multiphase regulation. Recently, much progress has been made in phase engineering, including the strategies of phase transition and applications of phase engineering in lithium/sodium storage. This Research Update summarizes the structure and electrical characteristics of transition metal compounds with multiple phases, various strategies for their phase transition engineering, and advanced applications in lithium/sodium storage. Moreover, we also offer general perspectives on current obstacles and future chances in this emerging field, including exploration on the sodium/lithium storage mechanism toward different phases, understanding on structure–mechanism–performance relationships in conjunction with theoretical and experimental research, development of new materials with phase transition and new phase transition strategies, and design of a phase interface (phase junction) with novel phase engineering. [ABSTRACT FROM AUTHOR]

Transition metal (TM) atoms have been extensively employed to decorate the two-dimensional materials, endowing them with promising physical properties. Here, we have studied the adsorption of TM atoms (V, Cr, Mn, Fe, and Co) on graphene-like zinc oxide monolayer (g-ZnO) and the substitution of Zn by TM using first-principles calculations to search for the most likely configurations when TM atoms are deposited on g-ZnO. We found that when a V atom is initially placed on the top of Zn atom, V will squeeze out Zn from the two-dimensional plane then substitute it, which is a no barrier substitution process. For heavier elements (Cr to Co), although the substitution configurations are more stable than the adsorption ones, there is an energy barrier for the adsorption-substitution transition with the height of tens to hundreds meV. Therefore, Cr to Co prefers to be adsorbed on the hollow site or the top of oxygen, which is further verified by the molecular dynamics simulations. The decoration of TM is revealed to be a promising approach in terms of tuning the work function of g-ZnO in a large energy range. [ABSTRACT FROM AUTHOR]

The two-dimensional (2D) magnet, a long-standing missing member in the family of 2D functional materials, is promising for next-generation information technology. The recent experimental discovery of 2D magnetic ordering in CrI3, Cr2Ge2Te6, VSe2, and Fe3GeTe2 has stimulated intense research activities to expand the scope of 2D magnets. This review covers the essential progress on 2D magnets, with an emphasis on the current understanding of the magnetic exchange interaction, the databases of 2D magnets, and the modification strategies for modulation of magnetism. We will address a large number of 2D intrinsic magnetic materials, including binary transition metal halogenides; chalogenides; carbides; nitrides; oxides; borides; silicides; MXene; ternary transition metal compounds CrXTe3, MPX3, Fe-Ge-Te, MBi2Te4, and MXY (M = transition metal; X = O, S, Se, Te, N; Y = Cl, Br, I); f-state magnets; p-state magnets; and organic magnets. Their electronic structure, magnetic moment, Curie temperature, and magnetic anisotropy energy will be presented. According to the specific 2D magnets, the underlying direct, superexchange, double exchange, super-superexchange, extended superexchange, and multi-intermediate double exchange interactions will be described. In addition, we will also highlight the effective strategies to manipulate the interatomic exchange mechanism to improve the Curie temperature of 2D magnets, such as chemical functionalization, isoelectronic substitution, alloying, strain engineering, defect engineering, applying electronic/magnetic field, interlayer coupling, carrier doping, optical controlling, and intercalation. We hope this review will contribute to understanding the magnetic exchange interaction of existing 2D magnets, developing unprecedented 2D magnets with desired properties, and offering new perspectives in this rapidly expanding field. [ABSTRACT FROM AUTHOR]

The pressure effects on melting temperatures of transition metals have been studied based on the combination of the modified Lindemann criterion with statistical moment method in quantum statistical mechanics. Numerical calculations have been performed for five transition metals including Cu, Pd, Pt, Ni, and Mn up to pressure 100 GPa. Our results are in good and reasonable agreements with available experimental data. This approach gives us a relatively simple method for qualitatively calculating high-pressure melting temperature. Moreover, it can be used to verify future experimental and theoretical works. This research proposes the potential of the combination of statistical moment method and the modified Lindemann criterion on predicting high-pressure melting of materials. [ABSTRACT FROM AUTHOR]

Light-emitting electrochemical cells (LECs) have received increasing attention during recent years due to their simple architecture, based on solely air-stabile materials, and ease of manufacture in ambient atmosphere, using solution-based technologies. The LEC's active layer offers semiconducting, luminescent as well as ionic functionality resulting in device physical processes fundamentally different as compared with organic light-emitting diodes. During operation, electrical double layers (EDLs) form at the electrode interfaces as a consequence of ion accumulation and electrochemical doping sets in leading to the in situ development of a light-emitting p-i-n junction. In this paper, we comment on the use of impedance spectroscopy in combination with complex nonlinear squares fitting to derive key information about the latter events in thin-film ionic transition metal complex-based light-emitting electrochemical cells based on the model compound bis-2-phenylpyridine 6-phenyl-2,2'-bipyridine iridium(III) hexafluoridophosphate ([Ir(ppy)2(pbpy)][PF6]). At operating voltages below the bandgap potential of the ionic complex used, we obtain the dielectric constant of the active layer, the conductivity of mobile ions, the transference numbers of electrons and ions, and the thickness of the EDLs, whereas the transient thickness of the p-i-n junction is determined at voltages above the bandgap potential. Most importantly, we find that charge transport is dominated by the ions when carrier injection from the electrodes is prohibited, that ion movement is limited by the presence of transverse internal interfaces and that the width of the intrinsic region constitutes almost 60% of the total active layer thickness in steady state at a low operating voltage. [ABSTRACT FROM AUTHOR]

The density functional theory (DFT)+U method is an efficient and effective way to calculate the ground-state properties of strongly correlated transition metal compounds, with the effective U parameters typically determined empirically. Two ab initio methods have been developed to compute the U parameter based on either constrained DFT (CDFT) or unrestricted Hartree-Fock (UHF) theory. Previous studies have demonstrated the success of both methods in typical open-shell materials such as FeO and NiO. In this Communication we report numerical instability issues that arise for the CDFT method when applied to closed-shell transition metals, by using ZnO and Cu2O as examples. By contrast, the UHF method behaves much more robustly for both closed- and open-shell materials, making it more suitable for treating closed-shell transition metals, as well as main group elements. [ABSTRACT FROM AUTHOR]

We study the transport properties of monolayer MX2 (M = Mo, W; X = S, Se, Te) n- and p-channel metal-oxide-semiconductor field effect transistors (MOSFETs) using full-band ballistic non-equilibrium Green's function simulations with an atomistic tight-binding Hamiltonian with hopping potentials obtained from density functional theory. We discuss the subthreshold slope, drain-induced barrier lowering (DIBL), as well as gate-induced drain leakage (GIDL) for different monolayer MX2 MOSFETs. We also report the possibility of negative differential resistance behavior in the output characteristics of nanoscale monolayer MX2 MOSFETs. [ABSTRACT FROM AUTHOR]

In this work, we have successfully developed plasma assisted paste sublimation route to deposit vertically aligned MoO3 nanoflakes (NFs) on nickel coated glass substrate in oxygen plasma ambience with the assistant of Ni thin layer as a catalyst. In our case, sublimation source (Mo strip surface) is resistively heated by flowing current across it. The structural, morphological, and optical properties of NFs have been investigated systematically using x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) with selected area electron diffraction (SAED), High resolution transmission electron microscopy (HRTEM), micro-Raman spectroscopy, and Photoluminescence (PL) spectroscopy. Studies reveal that the presence of oxygen plasma and the nickel thin layer are very essential for the growth of vertically aligned NFs. The observed results divulge that α-MoO3 NFs are deposited uniformly on large scale with very high aspect (height/thickness) ratio more than 30 and well aligned along [0 k 0] crystallographic direction where k is even (2, 4, 6). Raman spectrum shows a significant size effect on the vibrational property of MoO3 nanoflakes. The PL spectrum of MoO3 NFs was recorded at room temperature and four prominent peaks at 365 nm, 395 nm, 452 nm, and 465 nm corresponding to UV-visible region were observed. In this paper, a three step growth strategy for the formation of MoO3 NFs has been proposed in detail. [ABSTRACT FROM AUTHOR]

We apply a variant of the Hirshfeld density partitioning technique, HI, to calculate the atomic charges and decompose the dipole moments into the part due to the charges and the induced dipoles developed on each atom for three different transition metal (TM) containing molecules. Additionally, the α and β spin densities are treated separately developing a new variant (spin-adapted HI) of the fractional occupation HI version proposed recently. We also study the dependence of HI charges on the atomic state of the TM employed in the promolecule. The VO case exhibits a strong dependence of the atomic charge on the V or V+ state used. Although the bonding in the ground high spin electronic state and the first excited low spin state in TiO and VO is essentially identical, the dipole moments differ significantly and we find that this is due entirely to the σ electron distribution localized on the transition metal. Finally, the mechanism for the rapid change of the dipole moment of HScO upon bending is confirmed to occur mainly due to the induced atomic charges. [ABSTRACT FROM AUTHOR]

To develop a structural design that could provide accessible active sites to oxygen, electrolyte, and electron, it is necessary to modify the overall structure of an air electrode, which is considered as the most significant and complicated part of Zn–air batteries (ZABs). This review highlights the structural features essential to satisfy the design of the cathode compartment of ZABs and presents the associated factors that drive the oxygen reactions in the air electrode based on the relationship between the intrinsic activities of bifunctional O2 catalysts and the collective strategies employed to modify the electronic structure of such electrocatalysts. The first part describes the fundamentals of an ideal air electrode with its corresponding oxygen electrochemical reactions and typical bifunctional O2 catalysts. In-depth discussion of O2 catalysts for air electrodes and progress of binder-free air electrodes for ZABs are presented in the following based on three major modification strategies: defect engineering, cation/anion regulation in multi-components transition metal compounds, and single or multi-heteroatom doping in carbon materials (metal-free and metal-based material). The final part summarizes the properties of air electrodes needed to fulfill the requirements of electrically rechargeable ZABs and provides ideas for the future designs of air electrodes. [ABSTRACT FROM AUTHOR]

A new double-hybrid density functional, termed B2-PPW91, is presented which includes the Becke88 (B88) exchange in conjunction with Perdew-Wang91 (PW91) gradient-corrected correlation functional. The fitting parameters are obtained by minimization of mean absolute error of the static dipole polarizability of 4d transition metal monohalides against the CCSD(T)/aug-cc-pVTZ/SDD results. The performance of proposed functional has been assessed for estimation of other response properties, such as dipole moment and excitation energy, for the same species. We then proceed to explore the validity of B2-PPW91 method for calculation of the dipole polarizability of some 5d transition metal monofluorides. In all cases, the improvement compared to common density functional methods and even previously reported double-hybrid functionals such as B2-PLYP and mPW2-PLYP has been observed. This indicates that the utility of double-hybrid density functional methods can be further extended to study linear and non-linear optical properties of transition metal containing molecules. [ABSTRACT FROM AUTHOR]

A protocol has been developed for production of intense crystalloluminescence (XTL) from sodium chloride in aqueous solution by selective doping with transition metal salts (Ag+, Cu2+, and Dy3+). The method was used to record complete, fully dispersed deep UV-visible (200-650 nm) XTL spectra of sodium chloride for the first time. The results show conclusively that the emissions are due to dopant cations in the NaCl lattice, with no evidence for emission directly from NaCl, e.g., by triboluminescence resulting from crystalline fracture. The UV components of the XTL spectrum are attributed to single cation substituents (Ag+ and Cu+), and a strong visible component (∼415 nm) of the XTL is attributed to emission from silver-pair centers, (Ag+)2. The nature of the electronic transitions of the dopant cations is discussed. The results suggest that the timescale for transformation of a cluster to the crystalline phase is rapid, with efficient relaxation to the lowest excited electronic states of the dopant cation. This transformation is followed by photoemission of the cation in the nascent crystal. [ABSTRACT FROM AUTHOR]

The properties of the d-band structure of the transition metal atom in cubic LaBO3 and SrBO3 perovskites (where B = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) and their dependence on strain, d-band filling, and oxidation state were investigated using density functional theory calculations and atom-projected density of states. The strain dependence of the d-band width is shown to depend systematically on the size of the B atom. We show that the transition metal d-band width and center are linearly correlated with each other in agreement with a rectangular band model. A simple matrix element formalism based on the solid state table can readily predict the strain dependence of the d-band width. [ABSTRACT FROM AUTHOR]

Zinc bismuth vanadate glasses with compositions 50V2O5-xBi2O3-(50-x) ZnO have been prepared using a conventional melt-quenching method and the solubility limit of Bi2O3 in zinc vanadate glass system has been investigated using x-ray diffraction. Density has been measured using Archimedes' principle; molar volume (Vm) and crystalline volumes (Vc) have also been estimated. With an increase in Bi2O3 content, there is an increase in density and molar volume of the glass samples. The glass transition temperature (Tg) and Hurby coefficient (Kgl) have been determined using differential scanning calorimetry (DSC) and are observed to increase with increase in Bi2O3 content (i.e., x), up to x = 15, thereby indicating the structural modifications and increased thermal stability of zinc vanadate glasses on addition of Bi2O3. FTIR spectra have been recorded and the analysis of FTIR shows that the structure depends upon the Bi2O3 content in the glass compositions. On addition of Bi2O3 into the zinc vanadate system, the structure of V2O5 changes from VO4 tetrahedral to VO5 trigonal bi-pyramid configuration. The optical parameters have been calculated by using spectroscopic ellipsometry for bulk oxide glasses (perhaps used first time for bulk glasses) and optical bandgap energy is found to increase with increase in Bi2O3 content. [ABSTRACT FROM AUTHOR]

Early transition metal dichalcogenides (TMDC), characterized by their quasi-two-dimensional layered structure, have attracted intensive interest due to their versatile chemical and physical properties, but a comprehensive understanding of their structural and electronic properties from a first-principles point of view is still lacking. In this work, four simple TMDC materials, MX2 (M = Zr and Hf, X = S and Se), are investigated by the Kohn-Sham density functional theory (KS-DFT) with different local or semilocal exchange-correlation (xc) functionals and many-body perturbation theory in the GW approximation. Although the widely used Perdew-Burke-Ernzelhof (PBE) generalized gradient approximation (GGA) xc functional overestimates the interlayer distance dramatically, two newly developed GGA functionals, PBE-for-solids (PBEsol) and Wu-Cohen 2006 (WC06), can reproduce experimental crystal structures of these TMDC materials very well. The GW method, currently the most accurate first-principles approach for electronic band structures of extended systems, gives the fundamental band gaps of all these materials in good agreement with the experimental values obtained from optical absorption. The minimal direct gaps from GW are systematically larger than those measured from thermoreflectance by about 0.1-0.3 eV, implying that excitonic effects may be stronger than previously estimated. The calculated density of states from GW quasi-particle band energies agrees very well with photo-emission spectroscopy data. Ionization potentials of these materials are also computed by combining PBE calculations based on the slab model and GW quasi-particle corrections. The calculated absolute band energies with respect to the vacuum level indicate that that ZrS2 and HfS2, although having suitable band gaps for visible light absorption, cannot be used for overall water splitting as a result of mismatch of the conduction band minimum with the redox potential of H+/H2. [ABSTRACT FROM AUTHOR]

Based on semiempirical generalized embedded atom method (GEAM), we carried out molecular dynamics and Monte Carlo simulations to study the structural properties of FeCo and FeNi nanoparticles. It is found that these two kinds of nanoparticles possess a new stable quasicore-shell structure, no matter whether they are in molten or condensed state and whether they are prepared by annealing or quenching. In FeCo (FeNi) nanoparticles of various sizes and atom compositions, the quasicore-shell structure is always preferred, with the shell formed only by Fe atoms and the core formed by randomly distributed Co(Ni) and Fe atoms. We have also investigated the formation mechanism of the quasicore-shell structure by energy difference analysis of the pure and doped icosahedra structure of FeCo and FeNi nanoparticles. [ABSTRACT FROM AUTHOR]