Isostructural Systems Research Articles

Structural analysis and photocatalytic activities of bismuth-lanthanide oxide perovskites

A series of pure bismuth-lanthanide oxide perovskites of the formula of BiLnO3 (Ln = Sm, Eu, Tb, Er and Ho) has been synthesized via simple sol-gel methods. The elemental compositions and valence states of these materials were confirmed by X-ray photoelectron spectroscopy (XPS). Powder X-ray diffraction spectroscopy (PXRD) revealed an isostructural cubic system of BiEuO3, BiTbO3 BiErO3 and BiHoO3, whereas BiSmO3 adapted a rhombohedral system. Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) were employed to further characterize and analyze the structure of these mixed metal oxides. Band gap measurements obtained using diffuse reflectance spectroscopy (DRS) revealed potential photocatalytic activities of BiLnO3 in the visible light region (2.14 eV, 2.23 eV, 1.50 eV, 2.10 eV and 2.13 for BiSmO3, BiEuO3, BiTbO3, BiErO3 and BiHoO3 respectively). Accordingly, the photocatalytic performances of BiLnO3 were investigated for the cyclic carbonate formation by CO2 cycloaddition reaction to multiple epoxides. Reaction yields of the reported photocatalysts varied up to 99.9% depending on the epoxide substrate used. The simple sol-gel route explained in this report offers an easy, low-cost, environmentally friendly synthesis of highly efficient photocatalysts for a potential variety of photochemical reactions.

Structure of the Local Environment and Hyperfine Interactions of <sup>57</sup>Fe Probe Nuclei in AMnO<sub>3</sub> (A = Sc, In)

The results of a Mössbauer study of hyperfine interactions of 57Fe probe nuclei in isostructural hexagonal manganites h-ScMnO3 and h-InMnO3 are presented. The results of measurements of the Mössbauer spectra at T TN, as well as calculations of the parameters of the electric field gradient tensor at 57Fe nuclei, demonstrated different behavior of the probe iron ions in these isostructural systems, reflecting the difference in the processes of defect formation in their crystal lattices. On the contrary, measurements at T TN did not reveal any differences in the local magnetic structure of 57Fe probe atoms in these oxides.

Impact of Cr–O hybridization in ACrO3 (A = La, Y): A theoretical investigation

Electronic properties of spin polarized antiferromagnetic ACrO3 (A = La, Y) are explored with Hubbard model using density functional theory (DFT). These two isostructural systems are investigated using the different Hubbard energy and analyzed the hybridization of chromium 3d orbitals and oxygen 2p orbitals and the change in energy bandgaps against the Hubbard energy. The bond length and bond angle affect significantly the orbital contributions of Cr-3d and O-2p electrons for both the system. We noticed that the Cr–O hybridization affects the orbital degeneracy and is substantiated with partial density of states. These results emphasize the contribution of Hubbard energy in correlated electron systems.

So Close, Yet so Different: How One Donor Atom Changes Significantly the Photophysical Properties of Mononuclear Cu(I) Complexes.

The manipulation of the photophysical properties of molecular emitters can be realized by composing the close environment of the metal center with the "heavier pnictogen atom" effect. Replacing a nitrogen atom with a heavier phosphorus atom in otherwise isostructural molecular systems results in a significant change of the photophysical parameters. Herein, we report on the synthesis of four pairs of novel phosphinine-based and isostructural diimine-based Cu(I) complexes, which feature peculiar photophysical properties, and show how these parameters depend on the "heavier pnictogen atom" effect. The obtained Cu(I) complexes show triplet luminescence with MLCT character, which was investigated by means of spectroscopic and computational methods. It has been found that the photophysical properties of the coordination compounds show a dependency on the rigidity of the ancillary phosphine ligand in an unexpected manner. Replacing the nitrogen atom with a heavier phosphorus atom in otherwise isostructural molecular systems results in a significant change in emission energy and especially in the lifetime of the excited state. The results obtained demonstrate an efficient approach to the design of emissive molecular materials, which allows the construction of luminescent complexes with controlled photophysical properties.

Integration of Trinuclear Triangle Copper(II) Secondary Building Units in Octacyanidometallates(IV)-Based Frameworks.

The design and synthesis of high-dimensional materials based on secondary building blocks (SBUs) play a pivotal role in the further development of functional molecular materials. Herein, the self-assembly of Cu(II) ions, pyrazole (Hpz), and octacyanidometallate(IV) anions in the presence of water produced two new isostructural three-dimensional systems {[Cu3(μ3-OH)(μ-pz)3(H2O)3]2[M(CN)8]}·nH2O (M = W, 1, and Mo, 2). 1 and 2 consist of trinuclear triangle copper(II) (TTC) SBUs and octacyanidometallates(IV). At room temperature, both assemblies display strong antiferromagnetic interactions within the TTC entities with an average CuII···CuII isotropic magnetic coupling constant of about -145 cm-1. Moreover, a detailed analysis of magnetic data revealed the presence of spin frustration with antisymmetric magnetic exchange-coupling constants of around +32 and +46 cm-1 for 1 and 2, respectively. Finally, quantum chemical calculations explained their magnetic and optical properties.

Influence of Metal Identity on Light-Induced Switchable Adsorption in Azobenzene-Based Metal-Organic Frameworks.

Energy-efficient capture and release of small gas molecules, particularly carbon dioxide (CO2) and methane (CH4), are of significant interest in academia and industry. Porous materials such as metal-organic frameworks (MOFs) have been extensively studied, as their ultrahigh porosities and tunability enable significant amounts of gas to be adsorbed while also allowing specific applications to be targeted. However, because of the microporous nature of MOFs, the gas adsorption performance is dominated by high uptake capacity at low pressures, limiting their application. Hence, methods involving stimuli-responsive materials, particularly light-induced switchable adsorption (LISA), offer a unique alternative to thermal methods. Here, we report the mechanism of a well-known LISA system, the azobenzene-based material PCN-250, for CO2 and CH4 adsorption. There is a noticeable difference in the LISA effect dependent on the metal cluster involved, with the most significant being PCN-250-Al, where the adsorption can change by 83.1% CH4 and 56.1% CO2 at 298 K and 1 bar and inducing volumetric storage changes of 36.2 and 33.9 cm3/cm3 at 298 K between 5 and 85 bar (CH4) and 2 and 9 bar (CO2), respectively. Using UV light in both single-crystal X-ray diffraction and gas adsorption testing, we show that upon photoirradiation, the framework undergoes a "localized heating" phenomenon comparable to an increase of 130 K for PCN-250-Fe and improves the working capacity. This process functions because of the constrained nature of the ligand, preventing the typical trans-to-cis isomerization observed in free azobenzene. In addition, we observed that the degree of localized heating is highly dependent on the metal cluster involved, with the series of isostructural PCN-250 systems showing variable performance based upon the degree of interaction between the ligand and the metal center.

Spiral spin liquid behavior and persistent reciprocal kagome structure in frustrated van der Waals magnets and beyond

We study classical $J_1$-$J_2$ models with distinct spin degrees of freedom on a honeycomb lattice. For the XY and Heisenberg spins, the system develops a spiral spin liquid (SSL) that is a thermal cooperative paramagnetic regime with spins fluctuating around the spiral contours in the momentum space, and at low temperatures supports a vector spin-chirality order despite the absence of long-range magnetic order. In a strong contrast, for the Ising moments, the low-temperature spin correlation forms a reciprocal "kagom\'e" structure in the momentum space that resembles the SSL behaviors and persists for a range of exchange couplings. The unexpected emergence and persistence of the reciprocal "kagom\'e" are attributed to the stiffness of the Ising moments and the frustration. At higher temperatures when the thermal fluctuations is strong and the spin correlation is not fully melted, the reciprocal structures evolve from the "kagom\'e" towards the ones demanded by the soft spin limit. This contrasts strongly with the behaviors of the spiral contours in the SSL regime for the continuous spins. We suggest various experimentally relevant systems including van der Waals magnets such as the transition metal phosphorus trichalcogenides TMPX$_3$, Cr$_2$Ge$_2$Te$_6$, the rare-earth chalcohalides (like HoOF, ErOF and DyOF) and other isostructural systems to realize the SSL-like behaviors and/or the reciprocal kagom\'{e} structure.

Unconventional magnetic order emerging from competing energy scales in the new RRh3Si7 intermetallics ( R = Gd-Yb)

The competition between Ruderman-Kittel-Kasuya-Yosida (RKKY), crystal electric field (CEF), and Kondo energy scales has recently emerged at the heart of complex magnetism in several Ce- or Yb-based intermetallics. Hard axis magnetic order has been observed in a handful of these compounds, independent of the crystal symmetry, size of the ordered moment, or the relative scale of the Kondo and magnetic ordering temperatures. This raises the question of the role of each energy scale in driving the ground state properties. In focusing on a single class of compounds, the rhombohedral R${\mathrm{Rh}}_{3}{\mathrm{Si}}_{7}$, we compare the anisotropy and magnetic ground states in members of this series with only RKKY interactions (R = Gd), or RKKY and CEF effects (R = Tb-Tm), with the behavior of the R = Yb compound, where all three energy scales (RKKY, CEF, Kondo) are at play. Moreover, we extend the comparison to two other isostructural Kondo systems ${\mathrm{YbIr}}_{3}{\mathrm{Si}}_{7}$ and ${\mathrm{YbIr}}_{3}{\mathrm{Ge}}_{7}$, where hard axis magnetic order is also observed. The non-Kondo compounds R${\mathrm{Rh}}_{3}{\mathrm{Si}}_{7}$ (R = Tb-Tm) lack the complexity of magnetic order along the hard CEF axis, pointing to the dominant role of the Kondo effect in driving this magnetic order. However, the CEF-RKKY competition is still responsible for complex magnetic ground states, and it appears that the electronic and magnetic degrees of freedom are entangled in all magnetic members of this series of compounds.

Single-Component Molecular Conductors — Multi-Orbital Correlated π-d Electron Systems

Abstract Traditional molecular conductors are composed of more than two chemical species. Two prerequisites for the design of molecular metals have long been considered to be 1) forming of the electronic band and 2) existence of charge carriers created by the intermolecular charge transfer between the molecules constructing the band and other chemical species. On the other hand, a single-component molecular metal, [Ni(tmdt)2] (tmdt = trimethylenetetrathiafulvalenedithiolate), was developed in 2001; it is a planar nickel complex coordinated by the extended-TTF dithiolate ligands, tmdt from both sides. Since then, various types of single-component molecular conductors with a variety of extended-TTF dithiolate ligands have been developed. In this account, we briefly describe the recent progress in research on single-component molecular conductors. First, single-component molecular conductors in isostructural systems, [M(tmdt)2] (M = Ni, Pd, Pt, Au, and Cu) are described. Recent orbital-selective 13C and 1H NMR experiments have genealogically elucidated the differences in the electronic states and physical properties of these systems, that is, their various unusual phenomena are produced from their multi-orbital correlated π or π-d electron systems. Next, we describe [Ni(hfdt)2] (hfdt = bis(trifluoromethyl)tetrathiafulvalenedithiolate), the first single-component molecular superconductor, which was revealed by high-pressure resistivity measurements with a diamond anvil cell (DAC). The superconducting transition occurred around 7.5–8.7 GPa with a maximum Tc (onset temperature) of 5.5 K. Recent theoretical calculation has revealed that [Ni(hfdt)2] will be a new molecular Dirac electron system. In the final section, we briefly introduce molecular Dirac electron systems. Recently, a new series of semimetals, [M(dmdt)2] (M = Pt and Ni; dmdt = dimethyltetrathiafulvalenedithiolate) was synthesized. They belong to a three-dimensional ambient-pressure molecular massless Dirac electron system. The first-principles band structure calculations of [M(dmdt)2] (M = Pt and Ni) revealed that Dirac cones emerge along the a* direction and form Dirac nodal lines.

Hybrid Atomic Orbital Basis from First Principles: Bottom-Up Mapping of Self-Energy Correction to Large Covalent Systems.

Construction of hybrid atomic orbitals is proposed as the approximate common eigenstates of finite first moment matrices. Their hybridization and orientation can be a priori tuned as per their anticipated neighborhood. Their Wannier function counterparts constructed from the Kohn-Sham (KS) single particle states constitute an orthonormal multiorbital tight binding (TB) basis resembling hybrid atomic orbitals locked to their immediate atomic neighborhood, while spanning the subspace of KS states. The proposed basis thus renders predominantly single TB parameters from first principles for each nearest neighbor bond involving no more than two orbitals irrespective of their orientation and also facilitates an easy route for the transfer of such TB parameters across isostructural systems exclusively through mapping of neighborhoods and projection of orbital charge centers. With hybridized 2s, 2p and 3s, 3p valence electrons, the spatial extent of the self-energy correction (SEC) to TB parameters in the proposed basis is found to be localized mostly within the third nearest neighborhood, thus allowing effective transfer of self-energy-corrected TB parameters from smaller reference systems to much larger target systems, with nominal additional computational cost beyond that required for explicit computation of SEC in the reference systems. The proposed approach promises inexpensive estimation of the quasi-particle structures of large covalent systems with workable accuracy.

Isostructurality of quinoxaline crystal phases: the interplay of weak hydrogen bonds and halogen bonding

Creation of isostructural systems is a balance between thermodynamic and kinetic factors, shown by a set of substituted quinoxalines, where the lighter halogens form a set of metastable isostructural crystals, different to the heavy substitutions.

Electronic band structure of semiconductor alloys: From ab initio to k[formula omitted]p via computational alchemy, on example of [formula omitted] alloy

First principles calculations are increasingly often used in device modelling. However, due to their complexity and high computational costs, simplified but reliable models are of great value. In this work, we present an original method of finding the 30-band k·p parameters on an example of Ge1-xSnx alloy. It allows to reproduce the electronic band structure in the full BZ and in the full composition range. The method uses the state-of-the-art supercell based ab initio calculations as the reference. A direct fitting of the k·p parameters from ab initio supercell band structures is difficult since the assignment of the k·p bands to correct eigenvalues of the reference band structures may be ambiguous. For this reason, the ab initio computational alchemy is used as an intermediate step. Owing to its properties, the supercell unfolded eigenvalues are approximated with continuous curves, which enables a straigthforward way to fit the 30-band k·p parameters. As an example of application, the optical gain in bulk Ge0.91Sn0.09 has been calculated. The advantage of using the 30-band over the often used 8-band k·p approach is clearly seen. The presented method can be applied to any mixed, isovalent and isostructural system, eg. III-V, or II-VI alloys.

Symmetry induced phonon renormalization in few layers of 2H-MoTe2 transistors: Raman and first-principles studies

Understanding of electron–phonon coupling (EPC) in two-dimensional (2D) materials manifesting as phonon renormalization is essential to their possible applications in nanoelectronics. Here we report in situ Raman measurements of electrochemically top-gated 2, 3 and 7 layered 2H-MoTe2 channel based field-effect transistors. While the and B2g phonon modes exhibit frequency softening and linewidth broadening with hole doping concentration (p) up to ∼2.3 × 1013/cm2, A1g shows relatively small frequency hardening and linewidth sharpening. The dependence of frequency renormalization of the mode on the number of layers in these 2D crystals confirms that hole doping occurs primarily in the top two layers, in agreement with recent predictions. We present first-principles density functional theory analysis of bilayer MoTe2 that qualitatively captures our observations, and explain that a relatively stronger coupling of holes with or B2g modes as compared with the A1g mode originates from the in-plane orbital character and symmetry of the states at valence band maximum. The contrast between the manifestation of EPC in monolayer MoS2 and those observed here in a few-layered MoTe2 demonstrates the role of the symmetry of phonons and electronic states in determining the EPC in these isostructural systems.

In Situ Dynamics during Heating of Copper-Intercalated Bismuth Telluride

Summary The presence of a van der Waals gap within layered materials enables the intercalation of guest species, which can be used for tuning properties. The introduction of intercalant species may also lead to structural transformations across a range of temperatures and use conditions, but we have a limited understanding of the high-temperature evolution of intercalated layered materials. Here, we use in situ transmission electron microscopy to investigate temperature-dependent structural evolution of Bi2Te3, a layered material with well-known application as a thermoelectric, which contains intercalated Cu. As temperature is increased, the initially disordered Cu undergoes local ordering within the van der Waals gap, along with anisotropic sublimation behavior of the crystals. As the temperature is raised further, layered Cu2Te crystals nucleate and grow with a crystallographic relationship to the Bi2Te3 lattice. Notably, the presence of Cu decreases the thermal stability of the Bi2Te3 and substantially alters the transformation pathways during heating.

Oxygen vacancy enhanced ferroelectricity in BTO:SRO nanocomposite films

The enhancement of ferroelectric properties in lead-free ferroelectric is usually achieved by strain engineering. Here, we report a surprising polarization enhancement effect in an isostructural ferroelectric nanocomposite system composited by the ferroelectric material of BaTiO3 and metallic non-ferroelectric oxide of SrRuO3. BaTiO3:SrRuO3 (BTO:SRO) ferroelectric nanocomposite films with the volume ratio of nanogranular SRO ranging from 0 to 16% grown on the Nb-doped SrTiO3 (NSTO) single-crystal substrates by pulsed laser deposition (PLD) are investigated. Robust ferroelectric polarization is observed with a remanent polarization of about 40 μC/cm2, comparable to those found in Pb(ZrxTi1-x)O3 thin films. By combining X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), density functional theory (DFT) calculations, and phase-field simulation, a hypothesis has been proposed that the polarization enhancement may be mainly attributed to the accumulation of oxygen vacancies at the BTO/SRO interface rather than lattice mismatch strain. The novel mechanism of polarization enhancement opens new possibilities for designing future ferroelectric devices.

Temperature dependence of dynamic dipole formation in PbTe

PbTe-based thermoelectric materials remain of great interest due to their peculiar dynamic behavior and high thermoelectric performance. The true structure of pristine PbTe has been widely discussed, since the average rocksalt structure does not adequately account for the low lattice thermal conductivity. Single crystals of PbTe exhibit large amounts of x-ray diffuse scattering, which along with additional experimental observations has led to a series of structural models containing different types of disorder. Recently, analysis of the x-ray diffuse scattering from single-crystal PbTe confirmed the formation of local dynamic dipoles proposed earlier based on inelastic neutron scattering (INS) and one-dimensional pair distribution function (PDF) experiments. Here, we study the single-crystal diffuse x-ray scattering over a wider temperature range from 30 to 622 K in order to investigate the temperature dependence of the dynamic dipole formation. We observe that the longitudinal displacement correlations along the ⟨100⟩ directions form pairwise plateaus which results in a steplike decay of the correlations with increasing interatomic distance. This is consistent with previous observations from single-crystal diffuse scattering experiments on PbTe where the same steplike trend for the correlations was observed. However, upon lowering the temperature we observe a larger relative antiphase displacement contribution to the correlations proposed to originate from the softening of the transverse optical (TO) branch. As the local dipole formation depends on the absolute amplitude of antiphase displacements, and not the relative antiphase contribution to atomic displacements, it is found that the local dipole formation increases upon heating consistent with previous INS and PDF studies. The underlying mechanism responsible for the softening of the TO branch, and thereby the formation of dynamic dipoles, is investigated by comparison to the isostructural KCl system. The different dynamics in KCl and PbTe can be explained from the different bonding mechanism, where the metavalent bonding and ability to dynamically express a stereochemically active lone pair in PbTe gives rise to long-range interactions and TO phonon softening.

Experimental Estimate of the Holstein Electron–Phonon Coupling Constants in Perylene

AbstractA careful analysis of the vibrational spectra of two isostructural charge transfer systems with potential applications in optoelectronics, (perylene)3‐(TCNQF4)2, and (perylene)3‐(TCNQF2)2, highlights the presence of three strong infrared bands, polarized along the (perylene‐TCNQFx‐perylene) trimeric units present in the crystal. These bands are recognized as due to the Holstein, or electron–molecular vibration (e–mv) interaction. Use of appropriate modeling, based on the analysis of the frequency shifts due to the e–mv coupling, allows to extract the relevant Holstein coupling constants for the HOMO of the perylene molecule. The so‐obtained experimental values agree very well with density functional calculations, thus validating the results. The perylene relaxation energy, or small polaron binding energy, is about 70 meV, of the same order of magnitude as that of pentacene.

Electronic structure studies of FeSi: A chiral topological system

Most recent observation of topological Fermi arcs on the surface of manyfold degenerate B20 systems, CoSi and RhSi, have attracted enormous research interests. Although an another isostructural system, FeSi, has been predicted to show bulk chiral fermions, it is yet to be clear theoretically and as well experimentally that whether FeSi possesses the topological surface Fermi arcs associated with the exotic chiral fermions in vicinity of the Fermi level. In this contribution, using angle-resolved photoemission spectroscopy (ARPES) and density functional theory (DFT), we present the low-energy electronic structure of FeSi. We further report the surface state calculations to provide insights into the surface band structure of FeSi near the Fermi level. Unlike in CoSi or RhSi, FeSi has no topological Fermi arcs near the Fermi level as confirmed both from ARPES and surface state calculations. Further, the ARPES data show spin-orbit coupling (SOC) band splitting of 40 meV, which is in good agreement with bulk band structure calculations. We noticed an anomalous temperature dependent resistivity in FeSi which can be understood through the electron-phonon interactions as we find a Debye energy of 80 meV from the ARPES data.

Luminescence study of reduced samarium in barium lithium nonaborate and barium sodium nonaborate

Samarium doped barium lithium nonaborate and barium sodium nonaborate have been generated by firing stoichiometric mixtures of a co-precipitaed Sm(III):Ba(II) borate with lithium or sodium acetate and boric acid. The formation of the two isostructural systems was confirmed by Raman spectroscopy. Divalent samarium formation in both systems was confirmed by emission spectroscopy. The divalent samarium emission features characteristic of the two systems are reported and compared. Although known to be isostructural, significant variations are apparent in the emission patterns obtained from the two systems. However it is suggested that variations in the intensities of emission from two specific samarium sites give rise to the observed difference. The symmetries associated with the two samarium sites in barium lithium nonaborate have been suggested to be C4v and a distorted Oh.

Giant reversible barocaloric response of (MnNiSi)1−x(FeCoGe)x (x = 0.39, 0.40, 0.41)

MnNiSi-based alloys and isostructural systems have traditionally demonstrated impressive magnetocaloric properties near room temperature associated with a highly tunable first-order magnetostructural transition that involves large latent heat. However, these materials are limited by a small field-sensitivity of the transition, preventing significant reversible effects usable for cooling applications. Instead, the concomitant large transition volume changes prompt a high pressure-sensitivity, and therefore, promise substantial barocaloric performances, but they have been sparsely studied in these materials. Here, we study the barocaloric response in a series of composition-related (MnNiSi)1−x(FeCoGe)x (x = 0.39, 0.40, 0.41) alloys that span continuously over a wide temperature range around ambient. We report on giant reversible effects of ∼40 J K−1 kg−1 and up to ∼4 K upon application of ∼2 kbar and find a degradation of the first-order transition properties with pressure that limits the barocaloric effects at high pressures. Our results confirm the potential of this type of alloys for barocaloric applications, where multicaloric and composite possibilities, along with the high density and relatively high thermal conductivity, constructively add to the magnitude of the caloric effects.