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The energy materials performance is intrinsically determined by structures from the average lattice structure to the atom arrangement, valence, and distribution of the containing transition metal (TM) elements. Understanding the mechanism of the structure transition and atom rearrangement via synthesis or processing is key to expediting the exploration of excellent energy materials. In this work, in situ neutron scattering is employed to reveal the real-time structure evolution, including the TM–O bonds, lattice, TM valence and the migration of the high-voltage spinel cathode LiNi0.5Mn1.5O4. The transition-metal-mediated spinel destabilization under the annealing at the oxygen-deficient atmosphere is pinpointed. The formation of Mn3+ is correlated to the TM migration activation, TM disordered rearrangement in the spinel, and the transition to a layered-rocksalt phase. The further TM interdiffusion and Mn2+ reduction are also revealed with multi-stage thermodynamics and kinetics. The mechanisms of phase transition and atom migrations as functions of temperature, time and atmosphere present important guidance on the synthesis in various-valence element containing oxides.

Effects of Sc substitution on metamagnetic transitions for erbium are investigated for Er1–xScx (0.0 ≤ x ≤ 0.2) to find optimal magnetocaloric materials for high efficient magnetic refrigeration using static bias magnetic field. We observed that the Neel temperature decreases with increasing x. The magnetocaloric properties are discussed in comparison with the previously reported phase diagram. We found that the metamagnetic transitions from the antiferromagnetic-like configurations to the ferromagnetic-like ones are accompanied with relatively large magnetic entropy changes for all the samples. The obtained knowledge would be helpful to further study on magnetic refrigeration utilizing the features of metamagnetic transitions.

Doping enables manipulation of both the electrical and optical properties of halide perovskites. Herein, we incorporated Te4+ into Cs2ZrCl6 single crystal, simultaneously preserving the vacancy-ordered structure, to obtain an efficient yellow-emitting perovskite with a near-unity photoluminescence quantum yield (PLQY ≈ 97.6%). Te4+ doping modifies the hue and emission color of pristine Cs2ZrCl6, generates new absorption channels, and successfully extends the excitation energy from

Here we experimentally demonstrate the propagation of magnetostatic surface spin wave in the orthogonally joined yttrium iron garnet stripes in the form of T-shaped connection. By the means of microwave spectroscopy technique, we show how the transmission is affected by the distance between orthogonal yttrium iron garnet stripes. Micromagnetic modeling demonstrates the presence of nonreciprocal propagation of spin waves between all three ports of the T-junction. A mechanism for controlling the spatial-frequency selection of a propagating signal by variation of the air gap in the area of connected orthogonal sections is shown. The proposed structure can act as magnonic splitter for three-dimensional topology of multilevel magnonic networks. The transition to a multilayer topology of magnonic networks opens the possibility of increase of the packing density of computational units based on the principles of magnonics.

Silicene nanoribbons have been studied a lot in recent years, it is a nanostructure with enormous applications. The doping of another element into the unit cell changes the electrical and magnetic properties of the material, which creates new research directions in materials science. Based on the DFT theory, this work studies the doping phosphorus atoms and in silicene nanoribbons in the presence of an external electric field of about 0.1 V/Angstrom. The work also limited the doping study in two cases: The doping case of one phosphorus atom and the 100% doping configuration. There are two doping positions of a phosphorus atom, the top position, and the valley position, and the formation energy will find the optimal position. The energy band structure and state density will also be drawn, examined, and compared.

In metal-N-C systems, doped metals have an obvious valence change in the process of Li-ion deintercalation, which is in agreement with the operational principle of traditional anode materials. Doped metals will transfer some electrons to the neighboring N atoms to improve the valence state. Along with Li adsorption, the charge transferred to the nearest N or C from Li is less compared to that transferred to the doped metal. Hence, doped metals have an obvious valence change in the process of Li-ion deintercalation, and doped N just serves as a container for holding electrons. The local states of C and N p electrons in the Co-N-C structure can be fully destroyed, which can effectively improve the electronic properties of graphene.

Appropriate control of impurities from all sources is critically important during the development of a pharmaceutical product. One class of impurity that has gained considerable attention over the ...

Spin-vibronic coupling leads to spin relaxation in paramagnetic molecules, and an understanding of factors that contribute to this phenomenon is essential for designing next-generation spintronics technology, including single-molecule magnets and spin-based qubits, wherein long-lifetime magnetic ground states are desired. We report spectroscopic and magnetic characterization of the isoelectronic and isostructural series of homoleptic zerovalent transition metal triad M(CNDipp)6 (M = V, Nb, Ta; CNDipp = 2,6-diisopropylphenyl isocyanide) and show experimentally the significant increase in spin relaxation rate upon going from V to Nb to Ta. Correlated electronic calculations and first principle spin-phonon computations support the role of spin-orbit coupling in modulating spin-phonon relaxation. Our results provide experimental evidence that increasing magnetic anisotropy through spin-orbit coupling interactions leads to increased spin-vibronic relaxation, which is detrimental to long spin lifetime in paramagnetic molecules.

Substitutional metal doping is a powerful strategy for manipulating the emission spectra and excited state dynamics of semiconductor nanomaterials. Here, we demonstrate the synthesis of colloidal manganese (Mn

To explore alternative approaches to the CO2 reduction to formate and provide an insight into the spin state effect on the CO2 reduction, we theoretically designed a kind of low-valence iron(I) model complex, whose doublet, quartet, and sextet states are denoted as 2Fe(I), 4Fe(I), and 6Fe(I), respectively. This complex is featured with an iron(I) center, which bonds to a 1,2-ethanediamine (en) and a 2-hydroxy-biphenyl group. Reaction mechanisms for the CO2 reduction to formate catalyzed by this iron(I) model complex were explored using density functional theory (DFT) computations. Studies showed that the univalent iron(I) compound can efficiently fix and activate a CO2 molecule, whereas its oxidized forms with trivalent iron(III) or bivalent iron(II) cannot activate CO2. For the iron(I) compound, it was found that the lowest spin state 2Fe(I) is the most favorable for the CO2 reduction as the reactions barriers involving 2Fe(I), 4Fe(I), and 6Fe(I) are 25.6, 37.2, and 35.9 kcal/mol, respectively. Yet, a photosensitizer-free visible-light-mediated high–low spin shift from 4Fe(I) and 6Fe(I) to 2Fe(I) is likely through the reverse intersystem crossing (RIC) because the 4Fe(I) and 6Fe(I) compounds have strong absorption in the visible-light range. Notably, the synergistic interaction between the hydrogen bonding from the auxiliary hydroxyl group in the 2-hydroxy-biphenyl moiety to CO2 and an intermediate five-membered ring promotes the proton transfer, leading to the formation of the −COOH moiety from CO2 and the Fe–O bond. With the addition of H2, one H2 molecule is split by the Fe–O bond and thus serves as H atom sources for both the CO2 reduction and the recovery of the auxiliary hydroxyl group. The present theoretical study provides a novel solution for the challenging CO2 reduction, which calls for further experimental verifications.

Supramolecular engineering bridges molecular assembly with macromolecular charge-transfer salts, promising the design to construct supramolecular architectures that integrate cooperative properties difficult or impossible to find in conventional lattices. Here, we report the crystal engineering design and kinetic growth of one-dimensional supramolecular wires composed of bis(ethylenedithio)tetrathiafulvalene (ET+) cation and polymeric Cu[N(CN)2]2- anion. A bulk ferromagnetic order is discovered for filling up the gap where strong ferromagnetism is missing in such ET molecule-based charge-transfer salts. Metallicity is induced by electric current from the semiconducting wire, which is attributed to strain effect by tuning its close molecular contact. This structural feature is evidenced through the combination of various mechanistic spectroscopic studies. Electric dipole is established from the close molecular contacts and is suggestive to stabilize ferromagnetic spin interaction through anions bridging spin sites. The breakthrough shown here provides a pathway to explore low-dimensional supramolecular materials exhibiting strong electron correlation, metallicity, and ferromagnetism.

The temperature-dependent (T-dependent) linewidth (ΓG) and frequency shift (ΔωG) of the G mode provide valuable information on the phonon anharmonicity of graphene-based materials. In contrast to the negligible contribution from electron-phonon coupling (EPC) to the linewidth of a Raman mode in semiconductors, ΓG in pristine graphene is dominated by EPC contribution at room temperature due to its semimetallic characteristics. This leads to difficulty in resolving intrinsic contribution from phonon anharmonicity to ΓG. Here, we probed the intrinsic phonon anharmonicity of heavily-doped graphene by T-dependent Raman spectra based on FeCl3-based stage-1 graphite intercalation compound (GIC), in which the EPC contribution is negligible due to the large Fermi level (EF) shift. The ΔωG and ΓG exhibit a nonlinear decrease and noticeable broadening with increasing temperature, respectively, which are both dominated by phonon anharmonicity processes. The contribution of phonon anharmonicity to ΓG of heavily-doped graphene decreases as the EF approaches to the Dirac point. However, the T dependence of ΔωG is almost independent on EF and qualitatively agrees with the theoretical result of pristine graphene. These results provide a deeper understanding of the role of phonon anharmonicity on the Raman spectra of heavily doped graphene.

A theoretical study of geometrical structures, electronic properties, and spectral properties of single-atom transition metal-doped boron clusters MB24 (M = Sc, V, and Mn) is performed using the CALYPSO approach for the global minimum search, followed by density functional theory calculations. The global minima obtained for the VB24 and MnB24 clusters correspond to cage structures. Interestingly, the global minima obtained for the ScB24 cluster tend to a three-ring tubular structure. Population analyses and valence electron density analyses reveal that partial electrons on transition-metal atoms transfer to boron atoms. The localized orbital locator of MB24 (M = Sc, V, and Mn) indicates that the electron delocalization of ScB24 is stronger than that of VB24 and MnB24, and there is no obvious covalent bond between doped metals and B atoms. The spin density and spin population analyses reveal that MB24 (M = Sc, V, and Mn) have different spin characteristics which are expected to lead to interesting magnetic properties and potential applications in molecular devices. The calculated spectra indicate that MB24 (M = Sc, V, and Mn) has meaningful characteristic peaks that can be compared with future experimental values and provide a theoretical basis for the identification and confirmation of these single-atom transition metal-doped boron clusters. Our work enriches the database of geometrical structures of doped boron clusters and can provide an insight into new doped boron clusters.

A procedure is developed for the growth of thick, conformal CdS shells that preserve the optical properties of 5 nm HgSe cores. The n-doping of the HgSe/CdS core/shell particles is quantitatively tuned through a simple postsynthetic Cd treatment, while the doping is monitored via the intraband optical absorption at 5 μm wavelength. Photoluminescence lifetime and quantum yield measurements show that the CdS shell greatly increases the intraband emission intensity. This indicates that decoupling the excitation from the environment reduces the nonradiative recombination. We find that weakly n-type HgSe/CdS are the brightest solution-phase mid-infrared chromophores reported to date at room temperature, achieving intraband photoluminescence quantum yields of 2%. Such photoluminescence corresponds to intraband lifetimes in excess of 10 ns, raising important questions about the fundamental limits to achievable slow intraband relaxation in quantum dots.

International audience; Doping of transition metals within a semiconductor quantum dot (QD) has a high impact on the optical and magnetic properties of the QD. In this study, we report the synthesis of Mn 2+-doped Ag−In−Ga−Zn−S (Mn:AIGZS) QDs via thermolysis of a dithiocarbamate complex of Ag + , In 3+ , Ga 3+ , and Zn 2+ and of Mn(stearate) 2 in oleylamine. The influence of the Mn 2+ loading on the photoluminescence (PL) and magnetic properties of the dots are investigated. Mn:AIGZS QDs exhibit a diameter of ca. 2 nm, a high PL quantum yield (up to 41.3% for a 2.5% doping in Mn 2+), and robust photo-and colloidal stabilities. The optical properties of Mn:AIGZS QDs are preserved upon transfer into water using the glutathione tetramethylammonium ligand. At the same time, Mn:AIGZS QDs exhibit high relaxivity (r 1 = 0.15 mM −1 s −1 and r 2 = 0.57 mM −1 s −1 at 298 K and 2.34 T), which shows their potential applicability for bimodal PL/magnetic resonance imaging (MRI) probes.

In this study, the electronic behavior and mechanical properties of the ferromagnetic chalcospinel manganese-based selenide (AgMn2Se4) which crystallized in face centered cubic structure with space group Fd3 ̅m and space number 227, were investigated. All ab initio calculations were carried out by Generalized Gradient Approximation (GGA) under spin polarization. For this composition, three different type magnetic orders were considered to detect the most stable magnetic character. For the given composition, the results of the computations indicate its ferromagnetic nature since this compound has a lower ground state energy in this magnetic order than in other magnetic phases. After determining the most energetically stable magnetic phase, the electronic behavior in this magnetic arrangement was examined. The observed electronic band structure under spin polarization of this compound shows that this selenide system is almost half-metallic material due to having small band gap (Eg = 0.09 eV) in the minority spin state. In addition, the mechanical stability was determined with the help of elastic constants which were also employed to determine the mechanical characteristics of this compound.

Copper sulfide nanoparticles represent a class of dual-functional materials whose optical properties are dominated by interband electronic transitions and intraband plasmon resonances, both of whic...

The Ti-doped bismuth telluride-based thermoelectric material was prepared by high-temperature smelting combined with powder metallurgy, and the electron and phonon transporting mechanism was studied by a combination of first-principle calculations and experimental tests. The results show that Ti doping will introduce impurity levels, and its 3d orbits could significantly increase the density of states near the Fermi level, thereby increasing the effective mass, carrier concentration, and electrical conductivity and reducing the Seebeck coefficient. Ti doping will introduce a larger stress field, increase phonon scattering, and reduce lattice thermal conductivity. The maximum ZT value of the sample reached 1.25 at 340 K, which is 21.36% higher than that of the undoped sample.

Organic Mott-insulators are abundant among molecular conductors and are relevant to many emerging properties such as insulator-to-metal transitions, superconductivity, multiferroics, spin-liquids, ...

Spin-dependent charge transmission or the so-called chirality-induced spin selectivity (CISS) effect was demonstrated in self-assembled chiral coordinated monolayers. Distinct from the previous CISS phenomenon observed mainly on pure biomolecules, here we expanded this effect to the coordinated complex of chiral biomolecules and metal cations, specifically, cysteine-Cu2+-alanine (Cys/Cu/Ala), in which the complex itself was redox-active. However, the coordinated self-assembled monolayers of cysteine-Cu2+-cysteine did not show any spin-dependent effect. In addition, this phenomenon was explained by developing a theoretical model with spin-orbit coupling. The alanine molecules contributed to multiple transport pathways, leading to experimentally observable spin polarization. Finally, this CISS effect in Cys/Cu/Ala complex was demonstrated to amplify the sensing signal. The enantioselective discrimination efficiency could be improved by controlling the orientation of the external magnetic field.

The metal-organic framework Zr6O4(OH)4(bpydc)6 (bpydc2- = 2,2'-bipyridine-5,5'-dicarboxylate) is used to template the growth of a cluster fragment of the two-dimensional solid MnBr2, which was predicted to exhibit spin frustration. Single-crystal and powder X-ray diffraction analyses reveal a cluster with 19 metal ions arranged in a triangular lattice motif. Static magnetic susceptibility measurements indicate antiferromagnetic coupling between the high-spin (S = 5/2) MnII centers, and dynamic magnetic susceptibility data suggest population of low-lying excited states, consistent with magnetic frustration. Density functional theory calculations are used to determine the energies for a subset of thousands of magnetic configurations available to the cluster. The Yamaguchi generalized spin-projection method is then employed to construct a model for magnetic coupling interactions within the cluster, enabling facile determination of the energy for all possible magnetic configurations. The confined cluster is predicted to possess a doubly degenerate, highly geometrically frustrated ground state with a total spin of STotal = 5/2.

The exact diagonalization (ED) approach and Quantum Monte-Carlo (QMC) method were used for the study of the lowest energy states and low-temperature magnetic properties of some disordered 1D Heisenberg spin-1/2 systems formed by two types of three-spin structural units. For the system with a singlet ground state and the random distribution of structural units along the chain system, a significant decrease of the size of the intermediate magnetization plateau in comparison to the corresponding uniform spin system was found. For the “polyallyl” spin chain with a macroscopic value of the ground state spin, a transition to the singlet ground state due to the effect of compositional disorder was observed.

The hitherto unexplored surface structural and dynamical properties of the thermoelectric material β-Cu2S chalcocite, are uncovered using ab initio molecular dynamics simulations at 450 K. The material exhibits a hybrid crystalline-liquid behavior, with the liquidlike dynamics of the Cu atoms and the crystalline order of the sulfur sublattice. The topmost nanoscale region of the material is predicted to undergo significant structural relaxation, resulting in a ∼10% increase in the distance between the topmost S-layers accompanied by an increased Cu density. Cu diffusion in the interlayer regions of the surface S-sublattice is enhanced (doubled) compared to the bulk value, and an underlying microscopic mechanism, entailing marked emergent surface-induced softening of the S-sublattice vibrational dynamics, is described.

Chemical graph theory makes a connection between the sub-atomic structure of chemical compounds and mathematical models. Topological indices predict the physical properties of chemical compounds. T...

Here we propose new structures which can be represented as metallocene molecules organized into a 2D hybrid structure with two carbon layers and metal atoms sandwiched between them. We called them 2D metallocene-like structures or metal-intercalated bilayer graphene allotropes inspired by MCp2 structure. The Co and Fe metal atoms as filler between the carbon layers were considered. In addition to intriguing geometry, proposed structures show dynamical stability, which was studied by state-of-the-art computational techniques. The nature of metal-carbon bonding was determined and analyzed. Half-metallic properties were observed in the case of cobalt-containing structures. Localization of magnetic moments on individual cobalt atoms opens broad prospects for application in spintronics devices due to the shielding of a magnetic metal atom by the carbon network.

Two-dimensional (2D) Van der Waals ferromagnets carry the promise of ultimately miniature spintronics and information storage devices. Among the newly discovered 2D ferromagnets all inherit the magnetic ordering from their bulk ancestors. Here we report a new 2D ferromagnetic semiconductor at room temperature, 2H phase vanadium diselenide (VSe2) which show ferromagnetic at 2D form only. This unique 2D ferromagnetic semiconductor manifests an enhanced magnetic ordering owing to structural anisotropy at 2D limit.

Tetrahydrides crystallizing in the ThCr2 Si2 structure type have been predicted to become stable for a plethora of metals under pressure, and some have recently been synthesized. Through detailed first-principles investigations we show that the metal atoms within these I4/mmm symmetry MH4 compounds may be divalent, trivalent or tetravalent. The valence of the metal atom and its radius govern the bonding and electronic structure of these phases, and their evolution under pressure. The factors important for enhancing superconductivity include a large number of hydrogenic states at the Fermi level, and the presence of quasi-molecular H 2δ- units whose bonds have been stretched and weakened (but not broken) via electron transfer from the electropositive metal, and via a Kubas-like interaction with the metal. Analysis of the microscopic mechanism of superconductivity in MgH4 , ScH4 and ZrH4 reveals that phonon modes involving a coupled libration and stretch of the H 2δ- units leading to the formation of more complex hydrogenic motifs are important contributors towards the electron phonon coupling mechanism. In the divalent hydride MgH4 , modes associated with motions of the hydridic hydrogen atoms are also key contributors, and soften substantially at lower pressures.

Understanding the excited-state dynamics of nonfullerene electron acceptors is essential for further improvement of organic solar cells. Herein, we investigated the singlet and triplet excited-state dynamics in Y6, a novel nonfullerene acceptor, using transient absorption spectroscopy. We found that pristine Y6 films show biphasic singlet exciton decay kinetics with decay constants of ~220 ps and ~1200 ps, which is the origin of the large discrepancies in the previously reported exciton lifetimes in the solid state. The majority of the Y6 singlet excitons decayed with the faster (~220 ps) component, whereas a clear photoluminescence with the slower (~1200 ps) component was observed. Y6 singlet excitons undergo fast diffusion in the crystalline domains, resulting in fast singlet–singlet exciton annihilation, after which ultrafast triplet formation, assigned to singlet fission from higher excited singlet states, is observed.

A density functional theory + U systematic theoretical study was performed on the geometry, electronic structure, and energies of properties relevant for the chemical reactivity of TiO2 anatase. The effects of D3(BJ) dispersion correction and the Hubbard U value over the energies corresponding to the TiO2/Ti2O3 reduction reaction, the oxygen vacancy formation, and transition-metal doping were analyzed to attain an accurate and well-balanced description of these properties. It is suggested to fit the Hubbard correction for the metal dopant atom by taking as reference the observed low spin-high spin (HS) energy difference for the metal atom. PBEsol-D3 calculations revealed a distinct electronic ground state for the yttrium-doped TiO2 anatase surface depending upon the type of doping and interstitial or substitutional defects. Based on the calculations, it was found that a HS state explains the observed ferromagnetism in cobalt-substituted TiO2 anatase. The results presented herein might be relevant for further catalytic studies on TiO2 anatase using a large surface model that would be worthwhile for heterogeneous catalysis simulations.

Strain engineering of complex oxide heterostructures has provided routes to explore the influence of the local perturbations to the physical properties of the material. Due to the challenge of disentangling intrinsic and extrinsic effects at oxide interfaces, the combined effects of epitaxial strain and charge transfer mechanisms have been rarely studied. Here, we reveal the local charge distribution in manganite slabs by means of high-resolution electron microscopy and spectroscopy via investigating how the strain locally alters the electronic and magnetic properties of La0.5Sr0.5MnO3–La2CuO4 heterostructures. The charge rearrangement results in two different magnetic phases: an interfacial ferromagnetically reduced layer and an enhanced ferromagnetic metallic region away from the interfaces. Further, the magnitude of the charge redistribution can be controlled via epitaxial strain, which further influences the macroscopic physical properties in a way opposed to strain effects reported on single-phase films. Our work highlights the important role played by epitaxial strain in determining the spatial distribution of microscopic charge and spin interactions in manganites and provides a different perspective for engineering interface properties.

This work demonstrates that in parallel with the one existed at high doping concentration, there also exists an optimal combination of the transport properties of a thermoelectric material at low doping concentration as the curve of the relation between electrical conductivity and doping concentration is rigidly shifted toward that direction without disturbing the Seebeck coefficient and the thermal conductivity. Based on this finding, a new thermocouple design that uses low doping legs and high doping semiconductors as the external carrier injectors surrounding the legs is developed. The analytical model developed for the new thermocouple indicated that its efficiency and power output could be more than tripled as compared to those of the original design. A single thermocouple made of Silicon semiconductors was simulated numerically using different sets of input parameters. The results showed that the density of the externally injected carriers played a significant role in enhancing the thermocouple’s efficiency and power output.

Inverse weberites are of interest as geometrically frustrated magnetic materials due to their unique cation arrangement. We have synthesized nine isostructural materials that adopt the inverse weberite crystal structure, which consists of cross-linked kagome layers. These materials, having the general formula MIIMIIIF5(H2O)2 (MII = Co, Mn, Ni, Zn; MIII = Ga, Cr, Fe, V), were synthesized using mild hydrothermal conditions, which yielded phase-pure samples after optimization of the reaction conditions. Their crystal structures and optical, thermal, and magnetic behavior were characterized using single-crystal X-ray diffraction, UV-vis spectroscopy, thermogravimetric analysis, and measurement of the magnetic susceptibility and isothermal magnetization data, respectively. Three distinct types of magnetism were observed, including simple paramagnetism, antiferromagnetism, and canted antiferromagnetism; the last type is accompanied by a high frustration index fin the range 4.16-8.09. We demonstrated that the magnetic behavior of inverse weberites depends on the presence or absence of unpaired-electron-containing cations on the two distinct crystallographic sites, which can be employed for the prediction of the magnetic properties of other compounds in this rich and diverse family.

The article is devoted to the study of quantization of magnons in yttrium iron garnet film in the magnetic field gradient. Detected energy levels correspond to the quantization of particles in triangular potential. These energy levels are not equidistant. Therefore, they can be used to create a magnon quantum qubits.

Two-dimensional (2D) ferromagnetic materials are considered to be promising candidates for future generations of spintronic devices. Yet, 2D materials with intrinsic ferromagnetism are scarce. High-throughput first-principles simulations are performed in order to screen 2D materials that present a non-magnetic to a ferromagnetic transition upon hole doping. A global evolutionary search is subsequently performed, in order to identify alternative possible atomic structures of the eligible candidates, and 122 materials exhibiting hole-doping induced ferromagnetism are identified. Their energetic and dynamic stability, as well as their magnetic properties under hole doping, are investigated systematically. Half of these 2D materials are metal halides, followed by chalcogenides, oxides, and nitrides, some of them having predicted Curie temperatures above 300 K. The exchange interactions responsible for the ferromagnetic order in these 2D materials are also discussed. This work not only provides theoretical insights into hole-doped 2D ferromagnetic materials but also enriches the family of 2D magnetic materials for possible spintronic applications.

This paper reports the findings of spin density functional theory (DFT) calculations on the electronic properties of nitrogen (N)-doped (TiO2)33 nanocrystals as a function of different low-index fa...

The importance of spin-orbit effects on the predictions of energetic properties of actinide compounds has been considered for 18 different density functionals, comparing the spin-orbit and non-spin-orbit ("standard") forms of density functional theory (DFT). A set of enthalpies of formation for 66 small actinide (Th-Am) compounds-the An66 set, for which experimental data are available-have been investigated. The set includes actinide halides, oxides, and oxohalides in the general form AnOmXn, where n = 0-6, m = 0-3, and X = F, Cl, Br, or I. The impact of basis set choice was investigated, and to help account for the impact of relativity, the Stuttgart general and segmented contracted atomic natural orbital (ANO) basis sets paired with small core relativistic effective core potentials (RECP) as well as all-electron calculations utilizing the third-order Douglas-Kroll-Hess were considered.

Metal-Insulator-Metal (MIM) structures possess a number of shortcomings which include optical loss, tenability, nanofabrication challenges, chemical instability, incompatible manufacturing process etc. To overcome these shortcomings, plasmonic properties of heavily n-doped silicon are studied and found to be similar to those of conventional plasmonic metals like gold or silver. A plasmonic refractive index sensor using n-doped silicon instead of metal is designed and analyzed numerically using Finite Element Method (FEM). A maximum sensitivity of 4900 nm/RIU, which is higher than most of the MIM plasmonic refractive index (RI) sensors proposed to date, is obtained here. The RI sensor reported here, provides a significant improvement in the sensitivity of the device along with its compatibility with traditional nanoelectronics.

NdBaCo2O5 + δ, $$\delta \approx 0.5$$ , layered cobaltite is a metamagnet, which at a relatively low magnetic field transforms below T ~ 20 K from the antiferromagnetic phase to the mixed ferromagnetic state. Above T ~ 20 K, it is a mixture of exchange-coupled ferromagnetic and antiferromagnetic phases. The transition from the quasimetallic state to the state with a low electrical conductivity is accompanied by the spin-state transition in Со3+ ions from the HS/LS state to the IS/LS one.

The relative position of atomic planes of low-temperature monoclinic acanthite α-Ag2S and high-temperature bcc argentite β-Ag2S has been determined from X-ray and electron microscopy data. A reversible β‑Ag2S–α-Ag2S phase transition is due to the distortion of the bcc S sublattice in the structure of argentite β-Ag2S to the monoclinic sublattice of acanthite α-Ag2S. Distances between Ag atoms in cubic argentite are too small for the sites of the metal sublattice to be completely filled with Ag atoms. For this reason, the filling probabilities of sites of the metal sublattice is less than 0.1. Silver atoms in acanthite are at fairly large distances from each other because of monoclinic distortion and fill their positions with a probability close to 1. The relative orientations of the atomic planes of acanthite and argentite have been determined taking into account the displacements S and Ag atoms.

The connection between magnetism and superconductivity has long been discussed since the discovery of Fe-based superconductors. Here, we report the discovery of a pressure-induced transition from a spin to a superconducting state in novel MnN2 based on ab initio calculations. The superconducting state can be obtained in two ways: the first is the pressure-induced transition from an AFM-P21/m to an NM-I4/mmm phase at 30 GPa, while the other is the pressure-induced transition from an FM-I4/mmm phase to magnetic vanishing at 14 GPa, which leads to a structural transition with the distortion of octahedrons to tetragonal pyramids. NM-I4/mmm-MnN2 is superconductive with Tc ≈ 17.6 K at 0 GPa. In the second way, electronic structure calculations indicate that the system transforms from a high-spin state to a low-spin state due to increasing crystal-field splitting, causing disappearance of magnetism; more electron occupancy around the Fermi level drives the emergence of superconductivity. Remarkably, I4/mmm-MnN2 can achieve mutual spin-to-superconducting state transformation by pressure. Moreover, the AFM-P21/m-MnN2 phase is extremely incompressible with the hardness above 20 GPa. Our results provide a reasonable and systematic interpretation for the connection between magnetism and superconductivity and give clues for achieving spin-to-superconducting switching materials with certain crystal features.

Perovskites compounds (ABO3) have found a great many applications due to the simplicity of the crystal structure, chemical composition, and synthesis methods. The properties of these compounds can be modified by doping at A or B sites. Pure and Ni-doped BaSnO3 perovskite materials have been synthesized by a solid-state technique. The x-ray diffraction pattern suggests the presence of a polycrystalline BaSnO3 cubic phase. Rietveld analysis was carried out with General Structure and Analysis System II software. A tiny nanorod-like growth pattern was observed when the Ni doping concentration is increased to 2 mol%. Raman analysis, x-ray photoelectron spectral studies, and electron spin resonance studies revealed the presence of oxygen vacancies. The substitution of tin by nickel ions and the presence of oxygen deficiency in the material can be the reason for the observed increase in magnetic moment with Ni doping. The nonlinear optical property obtained from the Z scan (open aperture) studies revealed the optical limiting nature of the synthesized samples. The observed nonlinear optical process in the prepared materials has potential applications in optical limiters and eye-protecting devices. The dielectric properties of the synthesized samples have also been investigated.

There is a great interest in doping of different types of nanoparticles (NPs) in the opto-electronic display devices including liquid crystal displays and polymer dispersed LCs. Doping of NPs into ...

Singlet fission is a carrier multiplication mechanism that could make silicon solar cells much more efficient. The singlet-fission process splits one high-energy spin-singlet exciton into two lower-energy spin-triplet excitons. We calculated the efficiency potential of three technologically relevant singlet-fission silicon solar cell implementations. We assume realistic but optimistic parameters for the singlet-fission material and investigate the effect of singlet energy and entropic gain. If the transfer of triplet excitons occurs via charge transfer, the maximum efficiency is 34.6% at a surprisingly small singlet energy of 1.85 eV. For the Dexter-type triplet energy transfer, the maximum efficiency is 32.9% at a singlet energy of 2.15 eV. For Förster resonance energy transfer (FRET), the triplet excitons are first transferred into a quantum dot, from which they then undergo FRET into silicon. For this transfer mechanism, the maximum efficiency is 28.% at a singlet energy of 2.33 eV. We show that the efficiency gain from singlet fission is larger the more efficient the silicon base cell is, which stands in contrast to tandem perovskite–silicon solar cells.

The nodal-line semimetals have recently gained attention as a promising material due to their exotic electronic structure and properties. Here, we investigated the structural evolution and physical properties of nodal-line semimetal ZrSiSe under pressure via experiments and theoretical calculations. An isostructural electronic transition is observed at ∼6 GPa. Upon further compression, the original tetragonal phase starts to transform into an orthorhombic phase at ∼13 GPa and the two phases coexist until the maximal experimental pressure. By analysis of the electronic band structure, we suggest that the significant changes in the Fermi surface contribute to the occurrence of the isostructural electronic transition. The results provide a new insight into the structure and properties of ZrSiSe.

Molecular terms of dioxygen and nitic oxide are presented. Electron spin resonance spectra of diatomic molecules corresponding to these terms are discussed. Gas-phase ESR can be a convenient method of monitoring paramagnetic pollutants in the atmosphere. We ran additional calculations in molecular physics for terms of these molecules and Zeeman transitions.

The optical and photocatalytic properties of CdS quantum dots doped with manganese ions are considered. The quantum dots were synthesized by the colloidal method in an aqueous medium with mercaptoacetic acid as stabilizer. The optical, dimensional, and paramagnetic properties of the obtained nanoparticles were studied. The photocatalytic properties of the quantum dots were studied in the model degradation of rhodamine B. The effect of the concentration of manganese ions and the temperature of the reaction mixture on the rate of photodegradation of the dye was studied.

The paper presents the research results of the temperature dependence of molar heat capacity at a constant pressure within the temperature range from 5 to 300 K for vanadium-based materials. The density of states is calculated for all the materials near the Fermi level. It is shown that for V3Si and V3Ge compounds the density of states correlates with the superconducting transition temperature. It is also found that the metal-insulator transition temperature lowers with increasing density of states in V2O3 and V1.973Me0.027O3 (Me – Al, Fe, Cr) compounds.

The discovery of conductive and magnetic two-dimensional (2D) materials is critical for the development of next generation spintronics devices. Coordination chemistry in particular represents a highly versatile, though underutilized, route toward the synthesis of such materials with designer lattices. Here, we report the synthesis of a conductive, layered 2D metal–organic kagome lattice, Mn3(C6S6), using mild solution-phase chemistry. Strong geometric spin frustration in this system mediates spin freezing at low temperatures, which results in glassy magnetic dynamics consistent with a rare geometrically frustrated (topological) spin glass. Notably, we show that this geometric frustration engenders a large, tunable exchange bias of 1625 Oe in Mn3(C6S6), providing the first example of exchange bias in a coordination solid or a topological spin glass. Exchange bias is a critical component in a number of spintronics applications, but it is difficult to rationally tune, as it typically arises due to structural disorder. This work outlines a new strategy for engineering exchange bias systems using single-phase, crystalline lattices. More generally, these results demonstrate the potential utility of geometric frustration in the design of new nanoscale spintronic materials., Classic exchange bias relies on a disordered interface between a ferromagnet and antiferromagnet, impeding the design of next generation systems. We show that magnetic disorder due to geometric frustration engenders a large, tunable exchange bias in the metal−organic kagome lattice, Mn3(C6S6). As Mn3(C6S6) is a topological spin glass, the exchange bias may be a tuning handle for exotic nonequilibrium states. This work designates designer metal−organic lattices as a platform for novel emergent physical phenomena.

Kondo effect is an interesting phenomenon in quantum many-body physics. Niobium (Nb) is a conventional superconductor important for many superconducting device applications. It was long thought that the Kondo effect cannot be observed in Nb because the magnetic moment of a magnetic impurity, e.g. iron (Fe), would have been quenched in Nb. Here we report an observation of the Kondo effect in a Nb thin film structure. We found that by co-annealing Nb films with Fe in Argon gas at above 400 $$^{\circ }$$ ∘ C for an hour, one can induce a Kondo effect in Nb. The Kondo effect is more pronounced at higher annealing temperature. The temperature dependence of the resistance suggests existence of remnant superconductivity at low temperatures even though the system never becomes superconducting. We find that the Hamann theory for the Kondo resistivity gives a satisfactory fitting to the result. The Hamann analysis gives a Kondo temperature for this Nb–Fe system at $$\sim $$ ∼ 16 K, well above the superconducting transition onset temperature 9 K of the starting Nb film, suggesting that the screening of the impurity spins is effective to allow Cooper pairs to form at low temperatures. We suggest that the mechanism by which the Fe impurities retain partially their magnetic moment is that they are located at the grain boundaries, not fully dissolved into the bcc lattice of Nb.

The crystallographic analysis of three modifications of CaCO3 – rhombohedral calcite ( $$R\bar{3}c$$ ), orthorhombic aragonite (Pmcn), and monoclinic vaterite (C2/c) – reveals different mechanisms of atomic ordering in the structures. An important role in the formation of a specific structure is played by the point symmetry of energetically stable atomic groups (templates) in the precrystallization phase, which depends on the crystallization conditions, impurities, and local heterogeneities. Then the template symmetry forms the structure symmetry by placing heavy atoms and mass centers of stable CO3 atomic groups mainly in special positions with fixed coordinates. The details of this crystal dynamics (the ordering of atomic positions by translational and point symmetries) are shown.