Structural Transition Research Articles

Thermodynamic modeling of pressure-dependent phase diagram in alkali metals Li, Na and K

The high-pressure behavior of the alkali metals has attracted much attention in both experimental and theoretical aspects. This study is focused on the thermodynamic optimization of the temperature and pressure dependence of the molar volumes, the compressibility and phase diagrams of Li, Na and K according to the CALPHAD method. The pressure- temperature phase diagrams of lithium, sodium and potassium up to 50-100 GPa were calculated using the obtained thermodynamic parameters. The available experimental data, such as extremely low melting temperatures at high pressure, pressure-induced structural transitions between simple bcc and fcc crystals and the molar volume changes with the increasing pressure, were well reproduced in our calculations. The good agreements between our calculations and the experiments assessed in the literature indicated that our thermodynamic parameters are reasonable. Our thermodynamic calculations would assist to understand the phase transitions and structural properties of alkali metals at high pressure.

The effects of 3D printing parameters, structural design and post-processing on the mechanical properties and corrosion resistance of SLMed ZK60 porous scaffolds

High-quality porous Mg alloy scaffolds show promise in repairing large segmental bone defects. In this study, the authors prepared porous ZK60 scaffolds using the selective laser melting (SLM) method with three different model structures: Gyroid (G), Diamond (D), and Dodecahedral (Do). The researchers investigated the structural refinement, mechanical properties, and corrosive properties of SLM-ed ZK60 by adjusting the 3D printing parameters, specifically the scanning speed and laser power. The results show that, with optimized process parameters of a scanning speed of 400mm/s and a laser power of 110W, the relative density of the prepared samples was higher than 97%. After post-processing with electrolytic polishing, the G model scaffolds showed a smooth structural transition and the largest surface area compared to the other two models. The electrolytic polishing treatment also improved the structural refinement of the 70% designed porosity, with an error of only 4.3%. Additionally, the Do model scaffolds exhibited the best mechanical properties, with a yield strength of up to 24MPa and an elastic modulus of up to 425MPa. Furthermore, after coating treatment, the corrosion rate decreased from 5.67mm/year to 1.34mm/year after 48hours. These results demonstrate the potential of SLM-ed porous scaffolds for biomedical applications.

Dysregulated DnaB unwinding induces replisome decoupling and daughter strand gaps that are countered by RecA polymerization.

The replicative helicase, DnaB, is a central component of the replisome and unwinds duplex DNA coupled with immediate template-dependent DNA synthesis by the polymerase, Pol III. The rate of helicase unwinding is dynamically regulated through structural transitions in the DnaB hexamer between dilated and constricted states. Site-specific mutations in DnaB enforce a faster more constricted conformation that dysregulates unwinding dynamics, causing replisome decoupling that generates excess ssDNA and induces severe cellular stress. This surplus ssDNA can stimulate RecA recruitment to initiate recombinational repair, restart, or activation of the transcriptional SOS response. To better understand the consequences of dysregulated unwinding, we combined targeted genomic dnaB mutations with an inducible RecA filament inhibition strategy to examine the dependencies on RecA in mitigating replisome decoupling phenotypes. Without RecA filamentation, dnaB:mut strains had reduced growth rates, decreased mutagenesis, but a greater burden from endogenous damage. Interestingly, disruption of RecA filamentation in these dnaB:mut strains also reduced cellular filamentation but increased markers of double strand breaks and ssDNA gaps as detected by in situ fluorescence microscopy and FACS assays, TUNEL and PLUG, respectively. Overall, RecA plays a critical role in strain survival by protecting and processing ssDNA gaps caused by dysregulated helicase activity in vivo.

Inclusion of Anion Additives in the Inner Solvation Shell to Regulate the Composition of Solid Electrolyte Interphase

AbstractAn innovative approach to electrolyte engineering in carbonate electrolytes is introduced by incorporating high donor number dual anion additives into the conventional electrolyte system (1 M NaPF6 EC:PC). The active engagement of anions in the primary solvation shell effectively hinders the reduction of solvent molecules by reducing the Lowest Unoccupied Molecular Orbital (LUMO) of Na+‐solvent‐anion complex as compared to the LUMO of pure solvents or Na+‐solvent complex. The participation of anions leads to the formation of a thinner and an inorganic‐rich Solid Electrolyte Interphase on the hard carbon anode enhancing Initial Coulombic Efficiency and significantly improving its kinetics. Moreover, the system with dual anion additives exhibits oxidative stability up to 4.5 V, effectively mitigating the undesired side reactions at high voltage operation of the layered sodium nickel manganese oxide cathode. The addition of dual anion additives proves instrumental in suppressing structural degradation and transition metal dissolution during the long cycling performance of the layered oxide cathode in a sodium‐ion full cell. The synergistic effects of this dual anion additive added electrolyte on both the anode and the cathode ultimately ensured prolonged cycling of the sodium‐ion full cell. The electrolyte engineering approach outlined in this study opens the door to advancing next‐generation high‐voltage sodium batteries.

Topological phase transition and tunable surface states in YBi

A unique co-existence of extremely large magnetoresistance (XMR) and topological characteristics in non-magnetic rare-earth monopnictides has stimulated intensive research on these materials. Yttrium monobismuthide (YBi) has been reported to exhibit XMR up to 105% but its topological properties still need clarification. Here we use the hybrid density functional theory to probe the structural, electronic, and topological properties of YBi in detail. We observe that YBi is topologically trivial semimetal at ambient pressure which is in accordance with reported experimental results. The topological phase transitions i.e. trivial to non-trivial are obtained with volumetric pressure of 6.5 GPa and 3% of epitaxial strain. These topological phase transitions are well within the structural phase transition of YBi (24.5 GPa). The topological non-trivial state is characterized by band inversions among Y-d band and Bi-p band at Γ- and X-point which is further verified with the help of surface band structure along (001) plane. The Z2 topological invariants are calculated with the help of product of parities and evolution of Wannier charge centers. The occurrence of non-trivial phase in YBi with a relatively small epitaxial strain, which a thin film geometry can naturally have, make it an ideal candidate to probe inter-relationship between XMR and non-trivial topology.

Effective model and electron correlations in trilayer nickelate superconductor La4Ni3O10.

Recently, signatures of superconductivity with critical temperature from 20 to 30 K have been reported in pressured trilayer nickelate La$_4$Ni$_3$O$_{10}$ through a pressure-induced structure transition. Here we explore the evolution of electronic structures and electronic correlations in different phases of La$_4$Ni$_3$O$_{10}$ under corresponding pressure regions, by using density functional theory (DFT) combined with dynamical mean-field theory (DMFT). Similar to bilayer superconductor La$_3$Ni$_2$O$_{7}$, the electronic bands in superconducting La$_4$Ni$_3$O$_{10}$ are dominated by Ni-3$d_{x^2-y^2}$ and 3$d_{z^2}$ orbits near the Fermi level, in contrast, the inner Ni-O plane in La$_4$Ni$_3$O$_{10}$ generates a doublet hole-pocket Fermi surfaces around the Brillouin-zone corner, meanwhile one branch of the Ni-$3d_{z^2}$ bands is pushed very close above the Fermi level, which can induce an electron pocket through small electron doping. The DFT+DMFT simulations suggest that the electronic correlations only give minor modification to the Fermi surfaces, meanwhile the Ni-$3d_{z^2}$ and 3$d_{x^2-y^2}$ states on outer Ni-O layers have considerable greater mass enhancements than on the inner layer. The sensitiveness of electronic structure under doping and unique layer dependence of correlation suggest a distinct superconducting mechanism with respect to bilayer La$_3$Ni$_2$O$_{7}$. Based on the DFT and DFT+DMFT simulations, we eventually derive a trilayer effective tight-binding model, which can produce rather precise electronic bands and Fermi surfaces, hence can serve as an appropriate model to further study the superconducting mechanism and paring symmetry in trilayer La$_4$Ni$_3$O$_{10}$.

Hairpin protein partitioning from the ER to lipid droplets involves major structural rearrangements.

Lipid droplet (LD) function relies on proteins partitioning between the endoplasmic reticulum (ER) phospholipid bilayer and the LD monolayer membrane to control cellular adaptation to metabolic changes. It has been proposed that these hairpin proteins integrate into both membranes in a similar monotopic topology, enabling their passive lateral diffusion during LD emergence at the ER. Here, we combine biochemical solvent-accessibility assays, electron paramagnetic resonance spectroscopy and intra-molecular crosslinking experiments with molecular dynamics simulations, and determine distinct intramembrane positionings of the ER/LD protein UBXD8 in ER bilayer and LD monolayer membranes. UBXD8 is deeply inserted into the ER bilayer with a V-shaped topology and adopts an open-shallow conformation in the LD monolayer. Major structural rearrangements are required to enable ER-to-LD partitioning. Free energy calculations suggest that such structural transition is unlikely spontaneous, indicating that ER-to-LD protein partitioning relies on more complex mechanisms than anticipated and providing regulatory means for this trans-organelle protein trafficking.

Phase Transition Control in Molecular Solids via Complementarity of Hydrogen-Bond Strength.

Phase transitions in molecular solids involve synergistic changes in chemical and electronic structures, leading to diversification in physical and chemical properties. Despite the pivotal role of hydrogen bonds (H-bonds) in many phase-transition materials, it is rare and challenging to chemically regulate the dynamics and to elucidate the structure-property relationship. Here, four high-spin CoIIcom-pounds were isolated and systematically investigated by modifying the ligand terminal groups (X = S, Se) and substituents (Y = Cl, Br).S-ClandSe-Brundergo a reversible structural phase transition near room temperature, triggering the rotation of 15-crown-5 guests and the swing between syn- and anti-conformation of NCX-ligands, accompanied by switchable magnetism. Conversely,S-BrandSe-Clretain stability in ordered and disordered phases, respectively. H-bonds geometric analysis andab initiocalculations reveal that the electronegativity of X and Y affects the strength of NY-ap-H···X interactions. Entropy-driven structural phase transitions occur when the H-bond strength is appropriate; otherwise, the phase stays unchanged if it is too strong or weak. This work highlights a phase transition driven by H-bond strength complementarity - pairing strong acceptor with weak donor andvice versa, which offers a straightforward and effective approach for designing phase-transition molecular solids from a chemical perspective.

Lattice Oxygen Activation through Deep Oxidation of Co4N by Jahn-Teller-active Dopants for Improved Electrocatalytic Oxygen Evolution.

Triggering the lattice oxygen oxidation mechanism is crucial for improving oxygen evolution reaction (OER) performance, because it could bypass the scaling relation limitation associated with the conventional adsorbate evolution mechanism through the directly formation of oxygen-oxygen bond. High-valence transition metal sites are favorable for activating the lattice oxygen, but the deep oxidation of pre-catalysts suffers from a high thermodynamic barrier. Here, taking advantage of the Jahn-Teller (J-T) distortion induced structural instability, we incorporate high-spin Mn3+ (t2g3eg1) dopant into Co4N. Mn dopants enable a surface structural transformation from Co4N to CoOOH, and finally to CoO2, as observed by various in-situ spectroscopic investigations. Furthermore, the reconstructed surface on Mn doped Co4N triggers the lattice oxygen activation, as evidenced experimentally by pH-dependent OER, tetramethylammonium cation adsorption and on-line electrochemical mass spectrometry measurements of 18O-labelled catalysts. In general, this work not only offers the introducing J-T effect approach to regulate the structural transition, but also provides an understanding about the influence of catalyst's electronic configuration on determining the reaction route, which may inspire the design of more efficient catalysts with activated lattice oxygen.

Synergetic Responses of Multiple Functions Induced by Phase Transition in Molecular Materials.

Materials that integrate magnetism, electricity and luminescence can not only improve the operational efficiency of devices, but also potentially generate new functions through their coupling. Therefore, multifunctional synergistic effects have broad application prospects in fields such as optoelectronic devices, information storage and processing, and quantum computing. However, in the research field of molecular materials, there are few reports on the synergistic multifunctional properties. The main reason is that there is insufficient awareness of how to obtain such material. In this brief review, we summarized the molecular materials with this characteristic. The structural phase transition of substances will cause changes in their physical properties, as the electronic configurations of the active unit in different structural phases are different. Therefore, we will classify and describe the multifunctional synergistic complexes based on the structural factors that cause the first-order phase transition of the complexes. This enables us to quickly screen complexes with synergistic responses to these properties through structural phase transitions, providing ideas for studying the synergistic response of physical properties in molecular materials.

Effects of (KMn)3+ co-doping on the negative thermal expansion property of In2W3O12

At room temperature, monoclinic In2W3O12 ceramics exhibits positive thermal expansion. However, it transforms into an orthorhombic phase above 253 ℃, and then stably exhibits negative thermal expansion (NTE). In this work, to improve the NTE performance and extend the NTE temperature range of In2W3O12, the KxMnxIn2-xW3O12(0≤x≤0.5) ceramics were synthesized via the solid-state reaction method. The effects of (KMn)3+ double cation co-doping on the composition, microstructure, and thermal expansion behaviors of In2W3O12 ceramics were studied using XRD, Raman, XPS, SEM, and TMA. The results show that (KMn)3+ cations can replace In3+ in In2W3O12 ceramics. As the (KMn)3+ doping amount increases, monoclinic In2W3O12 gradually changed into monoclinic KxMnxIn2-xW3O12. Meanwhile, the grains grow up and the density of KxMnxIn2-xW3O12 ceramics was increased. Pure monoclinic KxMnxIn2-xW3O12 ceramics were prepared when x rises to 0.25 and 0.4. Among them, the thermal expansion coefficient of K0.4Mn0.4In1.6W3O12 ceramics in 100–700 ℃ is as high as -17.83×10-6 ℃-1, which was significantly improved compared to In2W3O12 ceramics. In addition, the structural phase transition of In2W3O12 ceramics around 253 ℃ was gradually eliminated and the NTE temperature range was widened. Double cation (KMn)3+ co-doping effectively improves the NTE performance of In2W3O12.

Tardigrade secretory proteins protect biological structures from desiccation

Tardigrades, microscopic animals that survive a broad range of environmental stresses, express a unique set of proteins termed tardigrade-specific intrinsically disordered proteins (TDPs). TDPs are often expressed at high levels in tardigrades upon desiccation, and appear to mediate stress adaptation. Here, we focus on the proteins belonging to the secreted family of tardigrade proteins termed secretory-abundant heat soluble (“SAHS”) proteins, and investigate their ability to protect diverse biological structures. Recombinantly expressed SAHS proteins prevent desiccated liposomes from fusion, and enhance desiccation tolerance of E. coli and Rhizobium tropici upon extracellular application. Molecular dynamics simulation and comparative structural analysis suggest a model by which SAHS proteins may undergo a structural transition upon desiccation, in which removal of water and solutes from a large internal cavity in SAHS proteins destabilizes the beta-sheet structure. These results highlight the potential application of SAHS proteins as stabilizing molecules for preservation of cells.

Pressure-induced evolution of structures and phase transition of technetium diboride

Using the particle swarm optimization algorithm, we conducted an extensive search for the high-pressure stable structure of technetium diboride (TcB2) within the pressure range of 0–400 GPa. At zero pressure, the P63/mmc (hP6-TcB2) structure is considered the ground state configuration. As the pressure increases, a structural transition from hP6-TcB2 to P6/mmm (hP3-TcB2) occurs at approximately 174.9 GPa. We discuss the bonding between the two distinct phases and analyze the contribution of different atomic bonds to maintaining their structural stability. Meanwhile, the temperature–pressure phase diagram of TcB2 was successfully determined for the first time through the quasi-harmonic approximation method. It is predicted that the transition pressure from hP6-TcB2 to hP3-TcB2 can be reduced to about 164 GPa at a room temperature of 300 K. These results provide valuable insights into the behavior of TcB2 under different temperature and pressure conditions and open up new possibilities for exploring its potential applications in a variety of environments.

The Macroeconomic Role of New Energy Sources in the Transition of Global Energy Structure

This paper looks into the changing world scene of energy with respect to shifts from traditional to new energy sources. When the trends are examined against the backdrop of rapid industrialization, technological breakthroughs, and globalization, it is noticeable that traditional energy sources have major environmental impacts, including greenhouse gas pollution and various health risks. The study demonstrates that new and renewable energy options such as solar, wind, hydro, and geothermal power could play a leading role in reducing climate change effects and improving air and water quality. The discussion on the macroeconomic influences of these new energy sources, particularly on power generation and the automotive sector, can be seen as having transformative potential in supporting sustainable development objectives. Although the article acknowledges the growth in this sector, it also pinpoints impediments that hinder the new energy technologies, including technological youthfulness, limited infrastructure, and intermittent supply of energy. The strategy recommended as a whole consists of enhanced investment in research and development; a joined approach of politics; edification programs; and public promotion with an aim to solve these difficulties and to hasten the process of global transition into a sustainable energy sphere. The study indicates that while environmental concerns should be balanced against economic development and societal benefits when shaping future global energy systems.

Structural phase transition of G-type antiferromagnetic SrMnO3 under pressure

Abstract SrMnO3 is a versatile material with applications in transistors, supercapacitors, and spintronic devices. This study employs the DFT+U calculations to investigate the electronic and magnetic properties of two polymorphs: 4H-SrMnO3 and 3C-SrMnO3 under isotropic pressure conditions up to 60 GPa. A novel approach based on density functional perturbation theory (DFPT) is employed to precisely determine the on-site Hubbard U value, yielding a computed value of 4.552 eV, consistent with experimental reports. Below P = 14 GPa, the G-AFM phase of 4H-SrMnO3 is the most favored stable, and transitioning to the G-AFM phase of 3C-SrMnO3 beyond 14 GPa. Notably, we observed significant changes in the band gaps, exhibiting an increasing trend under isotropic pressure,
while the magnetic moments of the Mn sites exhibit a decreasing trend from ≈ 2.8 μB to ≈ 2.3 μB for P = 0 GPa and 60 GPa, respectively. The projected density of states (PDOS) reveals the p-d hybridization contributions between the 3d-Mn and 2p-O covalent bonds, along with d-d Mott Hubbard interactions within the localized 3d orbitals of neighboring Mn-Mn atoms. Furthermore, a decrease in the Mn1-O-Mn2 distance prompts enhanced charge transfer which was facilitated by ligand holes, leading to a noticeable decrease in the magnetic moment of the Mn site in the G-AFM phase of SrMnO3.

Understanding metal bonding.

This theoretical discussion covers several effects of metallic bonding based on a simple formula. It comes from the first steps in the Moment Method for calculating the local electronic structure of a solid (such as at a surface or in a random alloy), and depends on the square root of the total coordination number C of near neighbours. Each atom is covalently bonded to its cluster of near neighbours as a whole. The properties of metals touched on include malleability, crystal structure and phase transitions, vacancy formation energy, surface catalysis, surface reconstruction, graphite stability, and some aspects of the benzene molecule seen as an atomic metal ring. In most of these, the 'saturation' type of curvature of the square root function plays a crucial role. A short historical survey indicates the development of the ideas from Bloch (1929) to recent times.

Similarities and differences in the ordering at short and long ranges in a NaNbO3 based Pb-free smart system: a key to functional properties

In this study, we have investigated the crystal structure of the solid solution of antiferroelectric NaNbO3(NN) with ferroelectric Ba0.9Ca0.1TiO3(BCT), i.e. (1−x)NN- xBCT for 0⩽x⩽1.0 using High-resolution powder x-ray diffraction (HR-XRD) data, dielectric measurements in conjunction with Raman spectroscopic studies. The investigation of long-range structural phase transitions as a function of composition(x) using x-ray diffraction is complemented by short-range structural insights from Raman spectroscopy. The incorporation of BCT disrupts the delicate antiferroelectric ordering of NN and stabilizes various ferroelectric phases with increasing BCT content(x). At x = 0.10, the simultaneous presence of two ferroelectric phases viz., Pmc21 and Amm2, results in a threefold rise in remanent polarization compared to off-boundary compositions. The composition with higher BCT content (i.e. x⩾0.50 ) has shown the anomalous existence of two long-range cubic structures, both of which are characterized by Pm 3¯ m space group. In spite of having a two-phase long-range centrosymmetric structure, we have observed a slim Polarization vs. Electric field(P-E) hysteresis loop for 0.50⩽x⩽0.80 . This contrapositive behavior (i.e. hysteresis loop in a centrosymmetric structure) has been attributed to the correlations among local static polar distortions of rhombohedral type ascertained using Raman spectroscopy. The coexistence of two ferroelectric phases at room temperature(for x = 0.10) and a slim hysteresis loop (for 0.50⩽x⩽0.80 ) make these compositions potential ingredients for applications in ferroelectric memory and energy storage devices.

Optimized Decision-Making for Multi-Market Green Power Transactions of Electricity Retailers under Demand-Side Response: The Chinese Market Case Study

With the energy structure transition and the development of the green power market, the role of electricity retailers in multi-market green power trading has become more and more important. Particularly in China, where aggressive green energy policies and rapid market transformations provide a distinct context for such studies, the challenges are pronounced. Under demand-side response, electricity retailers face the uncertainty of users’ electricity consumption and incentives, which complicates decision-making processes. The purpose of this paper is to explore the optimization decision-making problem of multi-market green power trading for electricity retailers under demand-side response, with a special focus on the Chinese market due to its leadership in implementing substantial green energy initiatives and its potential to set precedents for global practices. We first construct a two-party benefit optimization model, which comprehensively considers the profit objectives for electricity retailers and utility maximization for users. Then, the model is solved by the Lagrange multiplier method and distributed subgradient algorithm to obtain the optimal solution. Finally, the effectiveness of the incentive optimization strategy under the multi-market to promote green power consumption and improve the profit of electricity retailers is verified by arithmetic simulation. The results of this study show that the incentive optimization strategy under multi-market, particularly within the Chinese context, is expected to provide a reference for electricity retailers to develop more flexible and effective trading strategies in the green power market and to contribute to the process of promoting green power consumption globally.

Raman scattering of TixV1‐xO2 thin films on (110) rutile TiO2 in the low and high temperature phase adjacent to the metal–insulator transition

AbstractVanadium dioxide (VO2) undergoes a reversible first‐order metal‐to‐insulator transition (MIT) from a high‐temperature metallic phase to a low‐temperature insulating phase at a critical temperature Tc of 68°C. The MIT is accompanied by a structural phase transition. In addition to the metallic high‐temperature rutile phase, several insulating phases may be involved depending on doping, interfacial stress, or external stimuli. Unambiguously identifying the crystal phases involved in the phase transition is of key interest from the point of view of application as well as fundamental science. We study the impact of Ti doping of VO2 thin films on (110) rutile TiO2 substrates. We conduct a careful analysis of structural properties by combining results of x‐ray diffraction, Raman spectroscopy, and transmission electron microscopy. The transition temperature Tc of the deposited thin films decreases with increasing Ti‐content. All our thin film samples undergo a structural phase transition from the monoclinic M1‐phase to the rutile R‐phase with increasing temperature without passing the intermediate monoclinic M2‐phase. A careful analysis of polarization and angle‐dependent Raman data reveals that, above Tc, the unit cell of the high‐temperature rutile TixV1‐xO2 phase is aligned with that of the rutile TiO2 substrate whereas, below Tc, 180°‐domains of the M1‐phase of TixV1‐xO2 are observed. The structural relationship between TiO2 substrate and the high respective low‐temperature phase of the TixV1‐xO2 determined by Raman spectroscopy is in excellent agreement with TEM results on these samples. Raman spectroscopy is a powerful tool for studying structural changes of VO2‐based samples in the vicinity of MIT.

Nonlinear Optical Effects of Hybrid Antimony(III) Halides Induced by Stereoactive 5s2 Lone Pairs and Trimethylammonium Cations.

Organic-inorganic hybrid metal halides have unique optical and electronic properties, which are advantageous in the study of nonlinear optical materials. To investigate the effect of stereoactive lone pair electrons and the induction of organic cations on the structure of hybrid antimony(III) halides on nonlinear optics, we synthesize two noncentrosymmetric hybrid antimony(III)-based halide single crystals (TMA)3Sb2X9 (TMA = NH(CH3)3+, X = Cl, Br) by a room-temperature slow evaporation method, and their single-crystal structures, phase transition, X-ray photoelectron spectroscopy, and energy-band structure calculations are studied. More importantly, second-harmonic generation results of (TMA)3Sb2X9 (X = Cl, Br) are about 0.7 and 0.8 × KH2PO4(KDP), respectively. Interestingly, (TMA)3Sb2Cl9 single crystals undergo a reversible structural transition from Pc (No. 7) at room temperature to P21/c (No. 14) at 400 K, while the (TMA)3Sb2Br9 single crystals belong to the noncentrosymmetric space group R3c (No. 161), which clarifies the previous results. This work not only deepens the understanding of the role in lone pair electrons and organic cations in the structural induction in antimony-based halide perovskite materials but also provides guidance for subsequent nonlinear optical explorations.