Intermediate-temperature Phase Research Articles

J_{eff}=1/2 Hyperoctagon Lattice in Cobalt Oxalate Metal-Organic Framework.

We report the magnetic properties of a cobalt oxalate metal-organic framework featuring the hyperoctagon lattice. Our thermodynamic measurements reveal the J_{eff}=1/2 state of the high-spin Co^{2+} (3d^{7}) ion and the two successive magnetic transitions at zero field with two-stage entropy release. ^{13}C-NMR measurements reveal the absence of an internal magnetic field in the intermediate temperature phase. Multiple field-induced phases are observed before full saturation at around 40T. We argue the unique cobalt oxalate network gives rise to the Kitaev interaction and/or a bond frustration effect, providing an unconventional platform for frustrated magnetism on the hyperoctagon lattice.

Structural properties, thermodynamic stability and reaction pathways for solid-state synthesis of Bi2WO6 polymorphs.

This study presents a density functional theory (DFT) investigation into the structural, electronic, and optical properties, thermodynamic stability, phase competition, and reaction pathways of Bi2WO6, a notable compound within the Aurivillius family of oxides. We examine three distinct polymorphs of Bi2WO6: the low-temperature orthorhombic phase (P1), the intermediate-temperature orthorhombic phase (P2), and the high-temperature monoclinic phase (P3). Electronic structure analysis indicates band gaps of 2.339 eV (P1), 2.312 eV (P2), and 2.128 eV (P3), with the valence band primarily composed of O 2p states and the conduction band of Bi 6p and W 5d states. Optical properties, including the dielectric function and absorption spectra, show distinct behaviors for each phase, particularly P3. Elastic and phonon property analyses confirm the mechanical and dynamical stability of all three phases, with the P1 phase exhibiting the highest bulk modulus and stiffness among the polymorphs. Our effective mass calculations suggest that the P3 phase may have better charge carrier mobility compared to the P1 and P2 phases. Structural optimizations reveal marginal differences in total energy among these phases, suggesting their potential coexistence or easy phase transitions under varying conditions. Detailed Gibbs free energy calculations confirm that the P1 phase is the most stable at low temperatures, in agreement with experimental data in the literature. We also construct a chemical reaction network to explore feasible reaction pathways for the solid-state synthesis of Bi2WO6 from Bi2O3 and WO3 precursors, identifying several low-cost reaction pathways, including both direct and multi-step routes involving intermediates such as Bi14WO24 and Bi2W2O9.

Investigation of the intermolecular origins of high and low heats of fusion in azolium salt phase change materials for thermal energy storage

Azolium salts are potential intermediate-temperature phase change materials. Crystallographic analysis shows that H-bonding along with other intermolecular interactions strongly influence the melting enthalpy of azolium salts.

The Anatomy of a Turbulent Radiative Mixing Layer: Insights from an Analytic Model with Turbulent Conduction and Viscosity

Turbulent radiative mixing layers (TRMLs) form at the interface of cold, dense gas and hot, diffuse gas in motion with each other. TRMLs are ubiquitous in and around galaxies on a variety of scales, including galactic winds and the circumgalactic medium. They host the intermediate-temperature gases that are efficient in radiative cooling, thus playing a crucial role in controlling the cold gas supply, phase structure, and spectral features of galaxies. In this work, we develop an intuitive analytic 1.5-dimensional model for TRMLs that includes a simple parameterization of the effective turbulent conductivity and viscosity and a piecewise power-law cooling curve. Our analytic model reproduces the mass flux, total cooling, and phase structure of 3D simulations of TRMLs at a fraction of the computational cost. It also reveals essential insights into the physics of TRMLs, particularly the importance of the viscous dissipation of relative kinetic energy in balancing radiative cooling as the shear Mach number approaches unity. This dissipation takes place both in the intermediate-temperature phase, which reduces the enthalpy flux from the hot phase, and in the cold phase, which enhances radiative cooling. Additionally, our model provides a fast and easy way of computing the column density and surface brightness of TRMLs, which can be directly linked to observations.

Hierarchical proliferation of higher-rank symmetry defects in fractonic superfluids

Symmetry defects, e.g., vortices in conventional superfluids, play a critical role in a complete description of symmetry breaking phases. In this paper, we develop the theory of symmetry defects in fractonic superfluids, i.e., spontaneously higher-rank symmetry (HRS) breaking phases initially proposed by Yuan et al. [Phys. Rev. Res. 2, 023267 (2020)] and by Chen et al. [Phys. Rev. Res. 3, 013226 (2021)]. By Noether's theorem, HRS is associated with the conservation law of higher moments, e.g., dipoles, quadrupoles, and angular moments. We establish finite-temperature phase diagrams by identifying a series of topological phase transitions via the renormalization group flow equations and Debye-H\"uckel approximation. Accordingly, a series of Kosterlitz-Thouless topological transitions are found to occur successively at different temperatures, which are triggered by proliferation of defects, defect bound states, and so on. Such a hierarchical proliferation brings rich phase structures. Meanwhile, a screening effect from sufficiently high density of defect bound states leads to instability and collapse of the intermediate temperature phases, which further enriches the phase diagrams. For concreteness, we consider a fractonic superfluid in which ``angular moments'' are conserved. We then present the general theory, in which other types of HRS can be analyzed in a similar manner. Further directions are present at the end of the paper.

Inelastic neutron scattering in the weakly coupled triangular spin tube candidate CsCrF4

We performed inelastic neutron scattering (INS) experiments to measure spin dynamics on a polycrystalline sample of a spin tube candidate CsCrF$_{4}$. The compound exhibits a successive phase transition from a paramagnetic phase through an intermediate temperature (IT) phase of a 120$^{\circ}$ structure to a low temperature (LT) phase of another 120$^{\circ}$ structure. Elaborate comparison between observed and calculated neutron spectra in LT phase reveals that the spin Hamiltonian is identified as antiferromagnetic spin tubes including perturbative terms of intertube interaction, Dzyaloshinskii-Moriya interaction, and single ion anisotropy. A phase diagram for the ground state is classically calculated. A set of parameters in the spin Hamiltonian obtained from the INS spectra measured in LT phase is quite close to a boundary to the phase of the 120$^{\circ}$ structure of IT phase. The INS spectra measured in IT phase is, surprisingly, the same as those in LT phase in the level of powder averaged spectra, even though the magnetic structures in IT and LT phases are different. Identical dynamical structures compatible with two different static structures are observed. No difference in the observed spectra indicates no change of the spin Hamiltonian with the temperature, suggesting that the origin of the successive phase transition being order-by-disorder mechanism.

Cluster Toroidal Multipoles Formed by Electric-Quadrupole and Magnetic-Octupole Trimers: A Possible Scenario for Hidden Orders in Ca5Ir3O12

Cluster multipole orderings composed of atomic high-rank multipole moments are theoretically investigated with a 5$d$-electron compound Ca$_5$Ir$_3$O$_{12}$ in mind. Ca$_5$Ir$_3$O$_{12}$ exhibits two hidden orders: One is an intermediate-temperature phase with time-reversal symmetry and the other is a low-temperature phase without time-reversal symmetry. By performing the symmetry and augmented multipole analyses for a $d$-orbital model under the hexagonal point group $D_{\rm 3h}$, we find that the 120$^{\circ}$-type ordering of the electric quadrupole corresponds to cluster electric toroidal dipole ordering with the electric ferroaxial moment, which can become the microscopic origin of the intermediate-temperature phase in Ca$_5$Ir$_3$O$_{12}$. Furthermore, based on ${}^{193}$Ir synchrotron-radiation-based M\"{o}ssbauer spectroscopy, we propose that the low-temperature phase in Ca$_5$Ir$_3$O$_{12}$ is regarded as a coexisting state with cluster electric toroidal dipole and cluster magnetic toroidal quadrupole, the latter of which is formed by the 120$^{\circ}$-type ordering of the magnetic octupole and accompanies a small uniform magnetization as a secondary effect. Our results provide a clue to two hidden phases in Ca$_5$Ir$_3$O$_{12}$.

Rotational Dynamics of Organic Cations in Formamidinium Lead Iodide Perovskites.

We report results from quasi-elastic neutron scattering studies on the rotational dynamics of formamidinium (HC[NH2]2+, FA) and methylammonium (CH3NH3+, MA) cations in FA1-xMAxPbI3 with x = 0 and 0.4 and compare it to the dynamics in MAPbI3. For FAPbI3, the FA cation dynamics evolve from nearly isotropic rotations in the high-temperature (T > 285 K) cubic phase through reorientations between preferred orientations in the intermediate-temperature tetragonal phase (140 K < T ⩽ 285 K) to an even more complex dynamics, due to a disordered arrangement of the FA cations, in the low-temperature tetragonal phase (T ⩽ 140 K). For FA0.6MA0.4PbI3, the dynamics of the respective organic cations evolve from a relatively similar behavior to FAPbI3 and MAPbI3 at room temperature to a different behavior in the lower-temperature phases where the MA cation dynamics are a factor of 50 faster as compared to those of MAPbI3. This insight suggests that tuning the MA/FA cation ratio may be a promising approach to tailoring the dynamics and, in effect, optical properties of FA1-xMAxPbI3.

The role of cooling induced by mixing in the mass and energy cycles of the solar atmosphere

ABSTRACT In many astrophysical systems, mixing between cool and hot temperature gas/plasma through Kelvin–Helmholtz-instability-driven turbulence leads to the formation of an intermediate temperature phase with increased radiative losses that drive efficient cooling. The solar atmosphere is a potential site for this process to occur with interaction between either prominence or spicule material and the solar corona allowing the development of transition region material with enhanced radiative losses. In this paper, we derive a set of equations to model the evolution of such a mixing layer and make predictions for the mixing-driven cooling rate and the rate at which mixing can lead to the condensation of the coronal material. These theoretical predictions are benchmarked against 2.5D MHD simulations. Applying the theoretical scalings to prominence threads or fading spicules, we found that as a mixing layer grows on their boundaries this would lead to the creation of transition region material with a cooling time of ∼100 s, explaining the warm emission observed as prominence threads or spicules fade in cool spectral lines without the requirement for any heating. For quiescent prominences, dynamic condensation driven by the mixing process could restore ∼18 per cent of the mass lost from a prominence through downflows. Overall, this mechanism of thermal energy loss through radiative losses induced by mixing highlights the importance for considering dynamical interaction between material at different temperatures when trying to understand the thermodynamic evolution of the cool material in the solar corona.

Molecular motion of imidazolium cations and phase transitions in (ImH)2KCo(CN)6 with double perovskite structure

Temperature dependence of 1H nuclear magnetic resonance spin–lattice relaxation time T1 of (ImH)2KCo(CN)6, ImH+: imidazolium cation, is reported. The asymmetric T1 minimum observed in intermediate-temperature phase between 198 and 112 K is analyzed assuming the Cole-Davidson distribution of correlation time. Temperature dependences of 14N nuclear quadrupole resonance frequencies and spin–lattice relaxation times are also reported. The phase transitions at 198 and 112 K are shown to be of second and first order, respectively. The 14N relaxation is shown to be governed by the electric field gradient fluctuation due to the in-plane reorientational motion of the imidazolium cations.

The Extended Diffusive Sachdev–Ye–Kitaev Model as a Sort of “Strange Metal”

The linear dependence on temperature of the resistivity in metals undergoing high‐temperature superconducting transition is a puzzle, which is generally attributed to non‐Fermi liquid behavior on a large range of temperature values. No particle and momentum conservation characterizes the 0 + 1 − d Sachdev–Ye–Kitaev model as a tractable non‐Fermi liquid starting paradigm, when extended to higher space dimensions. Due to the conformal symmetry breaking in the incoherent phase, Goldstone bosons arise, which provide energy diffusion in the lattice. The linear response to energy diffusion in the model is discussed, which is in principle charge neutral and non‐momentum conserving, and the temperature dependence of the thermal and electric conductivity in the incoherent prechaotic, intermediate temperature phase is obtained.

Phase stabilities and equilibria of the Ti-Al-Nb ternary system at intermediate temperatures I. The 900 °C isothermal section

Determination of intermediate temperature phase diagrams is a challenging task due to sluggish transformation kinetics, metastable phases and low diffusion coefficients encountered under these conditions. The development of Ti-Al-Nb alloys has been hampered by scarcity of intermediate temperature phase diagrams. Through guidance from diffusion simulation results, we designed the composition of the diffusion components in a diffusion multiple capable of efficiently and accurately testing the Ti-Al-Nb ternary phase diagrams at intermediate temperatures, which is the service temperature of Ti-Al-Nb alloys. We systematically characterized the diffusion multiples using scanning electron microscopy (SEM), electron probe microanalysis (EPMA), electron backscatter diffraction (EBSD), transmission kikuchi diffraction (TKD) and transmission electron microscope (TEM), and constructed the whole composition range of the 900 °C isothermal section. The constructed range includes ten stable phases, nineteen two-phase regions and ten three-phase regions. Two ternary phases (O-Ti2AlNb and ωo-Ti4Al3Nb phases) were determined and the ωo phase was defined on the experimental phase diagram for the first time. The previous thermodynamic database at 900 °C is unreliable, based on the present work. The present experimental results will bridge the existing research gap by providing the missing thermodynamic data. The present diffusion multiple is expected to construct more isothermal sections of Ti-Al-Nb ternary system at intermediate temperatures in the future. The constructed phase diagrams are also invaluable tools to researchers and industry for development of Ti-Al-Nb alloys.

Orientational order and phase transitions in deuterated methane: a neutron total scattering and reverse Monte Carlo study

We report a study of the orientational order and phase transitions in crystalline deuterated methane, carried out using neutron total scattering and the reverse Monte Carlo method. The resultant atomic configurations are consistent with the average structures obtained from Rietveld refinement of the powder diffraction data, but additionally enable us to determine the C–D bond orientational distribution functions (ODF) for the disordered molecules in the high-temperature phase, and for both ordered and disordered molecules in the intermediate-temperature phase. We show that this approach gives more accurate information than can been obtained from fitting a bond ODF to diffraction data. Given the resurgence of interest in orientationally-disordered crystals, we argue that the approach of total scattering with the RMC method provides a unique quantification of orientational order and disorder.

Emergent moments in a Hund's impurity

Motivated by the relevance of Hund's coupling in the context of multiorbital superconductors, we revisit the problem of a multiorbital Kondo impurity with Hund's interaction. Using dynamical large-N techniques, we propose an efficient approach that retains the essential physics at play, while providing a pathway to scalable quantum impurity solvers. We are able to follow the ground state, dynamic, and thermodynamic properties of this system over many decades of temperature. Our approach captures the emergence of large moments, and follows the stretched evolution of the physics down to their exponentially suppressed Kondo temperature. We focus our analysis on the intermediate finite temperature phase which presents an alternate paramagnetic state due to the emergent moment, and discuss the relevance of this regime to Hund's metals.

Stabilization of Ferroelectric Phase in Highly Oriented Quinuclidinium Perrhenate (HQReO4) Thin Films.

The low-temperature processability of molecular ferroelectric (FE) crystals makes them a potential alternative for perovskite oxide-based ferroelectric thin films. Quinuclidinium perrhenate (HQReO4) is one such molecular FE crystal that exhibits ferroelectricity when crystallized in an intermediate temperature phase (ITP). However, bulk HQReO4 crystals exhibit ferroelectricity only for a narrow temperature window (22 K), above and below which the polar phase transforms to a non-FE phase. The FE phase or ITP of HQReO4 should be stabilized in a much wider temperature range for practical applications. Here, to stabilize the FE phase (ITP) in a wider temperature range, highly oriented thin films of HQReO4 were prepared using a simple solution process. A slow evaporation method was adapted for drying the HQReO4 thin films to control the morphology and the temperature window. The temperature window of the intermediate temperature FE phase was successfully widened up to 35 K by merely varying the film drying temperature between 333 and 353 K. The strategy of stabilizing the FE phase in a wider temperature range can be adapted to other molecular FE materials to realize flexible electronic devices.

A Molecular Crystal Shows Multiple Correlated Magnetic and Ferroelectric Switchings

Simultaneous control of the magnetic and electric properties of materials is crucial for their application in next-generation memory and sensor devices. Herein, we report a single-crystal Co(II) co...

Silicon ISM X-ray absorption: the gaseous component

ABSTRACT We present a detailed analysis of the gaseous component of the Si K edge using high-resolution Chandra spectra of low-mass X-ray binaries. We fit the spectra with a modified version of the ISMabs model, including new photoabsorption cross-sections computed for all Si ionic species. We estimate column densities for Si i, Si ii, Si iii, Si xii, and Si xiii, which trace the warm, intermediate temperature, and hot phases of the Galactic interstellar medium. We find that the ionic fractions of the first two phases are similar. This may be due to the physical state of the plasma determined by the temperature or due to the presence of absorber material in the close vicinity of the sources. Our findings highlight the need for accurate modelling of the gaseous component before attempting to address the solid component.

Multiphase Gas and the Fractal Nature of Radiative Turbulent Mixing Layers

Abstract A common situation in galactic and intergalactic gas involves cold dense gas in motion relative to hot diffuse gas. Kelvin–Helmholtz instability creates a turbulent mixing layer and populates the intermediate-temperature phase, which often cools rapidly. The energy lost to cooling is balanced by the advection of hot high enthalpy gas into the mixing layer, resulting in growth and acceleration of the cold phase. This process may play a major role in determining the interstellar medium and circumgalactic medium phase structure, and accelerating cold gas in galactic winds and cosmic filaments. Cooling in these mixing layers occurs in a thin corrugated sheet, which we argue has an area with fractal dimension D = 5/2 and a thickness that adjusts to match the hot phase mixing time to the cooling time. These cooling sheet properties form the basis of a new model for how the cooling rate and hot gas inflow velocity depend on the size L, cooling time of the mixed phase , relative velocity , and density contrast of the system. Entrainment is expected to be enhanced in environments with short , large , and large . Using a large suite of three-dimensional hydrodynamic simulations, we demonstrate that this fractal cooling layer model accurately captures the energetics and evolution of turbulent interfaces and can therefore be used as a foundation for understanding multiphase mixing with strong radiative cooling.

Ground-state properties and lattice-vibration effects of disordered Fe-Ni systems for phase stability predictions

By means of density functional theory, we perform a focused study of both body-centered-cubic (bcc) and face-centered-cubic (fcc) Fe-Ni random solid solutions, represented by special quasirandom structures. The whole concentration range and various magnetic configurations are considered. Excellent agreement on the concentration dependence of magnetization is found between our results and experimental data, except in the Invar region. Some locally antiferromagnetic fcc structures are proposed to approach experimental values of magnetization. Vibrational entropies of ordered and disordered systems are calculated for various concentrations, showing an overall good agreement with available experimental data. The vibrational entropy systematically contributes to stabilize disordered rather than ordered structures and is not negligible compared to the configurational entropy. Free energy of mixing is estimated by including the vibrational and ideal configurational entropies. From them, low- and intermediate-temperature Fe-Ni phase diagrams are constructed, showing a better agreement with experimental data than the one from a recent thermodynamic assessment for some phase boundaries below 700 K. The determined order-disorder transition temperatures for the $\mathrm{L}{1}_{0}$ and $\mathrm{L}{1}_{2}$ phases are in good agreement with the experimental values, suggesting an important contribution of vibrational entropy.

Strong and fragile topological Dirac semimetals with higher-order Fermi arcs

Dirac and Weyl semimetals both exhibit arc-like surface states. However, whereas the surface Fermi arcs in Weyl semimetals are topological consequences of the Weyl points themselves, the surface Fermi arcs in Dirac semimetals are not directly related to the bulk Dirac points, raising the question of whether there exists a topological bulk-boundary correspondence for Dirac semimetals. In this work, we discover that strong and fragile topological Dirac semimetals exhibit one-dimensional (1D) higher-order hinge Fermi arcs (HOFAs) as universal, direct consequences of their bulk 3D Dirac points. To predict HOFAs coexisting with topological surface states in solid-state Dirac semimetals, we introduce and layer a spinful model of an s–d-hybridized quadrupole insulator (QI). We develop a rigorous nested Jackiw–Rebbi formulation of QIs and HOFA states. Employing ab initio calculations, we demonstrate HOFAs in both the room- (α) and intermediate-temperature (α″) phases of Cd3As2, KMgBi, and rutile-structure ( beta ^{prime} -) PtO2.