Unusual Temperature Dependence Research Articles

Ensemble Monte Carlo transport studies of zinc-blende cuprous halides

We present a comprehensive theoretical analysis of intrinsic high-field transport in cuprous halides: CuCl, CuBr, and CuI. Ensemble Monte Carlo transport simulations were performed based on analytical approximations of the multi-valley and three-band electronic structure model. The deformation potentials, extracted from carrier–phonon interaction matrix elements calculated via the Wannier function approach, were employed to determine scattering rates. Our detailed analysis uncovers intriguing transport characteristics based on the complex valence band structures, resulting from spin–orbit coupling and band inversion. Remarkably, the hole mobility in CuI was exceptionally high, reaching up to 193 cm2/V s, while CuCl exhibited unusual temperature dependencies in hole transport. Additionally, the electron mobility in CuI was found to be 254 cm2/V s, indicating a minimal disparity between carrier mobilities, which is advantageous for optoelectronic applications.

Unusual temperature dependence of thermal conductivity due to phonon resonance scattering by point defects in cubic BN

Unusual temperature dependence of thermal conductivity due to phonon resonance scattering by point defects in cubic BN

Roles of H-Bonding and Hydride Solvation in the Reaction of Hydrated (Di)electrons with Water to Create H2 and OH.

Even though single hydrated electrons (ehyd-'s) are stable in liquid water, two hydrated electrons can bimolecularly react with water to create H2 and hydroxide: ehyd- + ehyd- + 2H2O → H2 + 2OH-. The rate of this reaction has an unusual temperature and isotope dependence as well as no dependence on ionic strength, which suggests that cosolvation of two electrons as a single hydrated dielectron (e2,hyd2-) might be an important intermediate in the mechanism of this reaction. Here, we present an ab initio density functional theory study of this reaction to better understand the potential properties, reactivity, and experimental accessibility of hydrated dielectrons. Our simulations create hydrated dielectrons by first simulating single ehyd-'s and then injecting a second electron, providing a well-defined time zero for e2,hyd2- formation and offering insight into a potential experimental route to creating dielectrons and optically inducing the reaction. We find that e2,hyd2- immediately forms in every member of our ensemble of trajectories, allowing us to study the molecular mechanism of H2 and OH- formation. The subsequent reaction involves separate proton transfer steps with a generally well-defined hydride subintermediate. The time scales for both proton transfer steps are quite broad, with the first proton transfer step spanning times over a few ps, while the second proton transfer step varies over ∼150 fs. We find that the first proton transfer rate is dictated by whether or not the reacting water is part of an H-bond chain that allows the newly created OH- to rapidly move by Grotthuss-type proton hopping to minimize electrostatic repulsion with H-. The second proton transfer step depends significantly on the degree of solvation of H-, leading to a wide range of reactive geometries where the two waters involved can lie either across the dielectron cavity or more adjacent to each other. This also allows the two proton transfer events to take place either effectively concertedly or sequentially, explaining differing views that have been presented in the literature.

Unusual dynamics of tetrahedral liquids caused by the competition between dynamic heterogeneity and structural heterogeneity.

Tetrahedral liquids exhibit intriguing thermodynamic and transport properties because of the various ways tetrahedra can be packed and connected. Recently, an unusual temperature dependence of the stretching exponent β in a model tetrahedral liquid ZnCl2 from Tm + 85K to Tm + 35K has been reported using neutron-spin echo spectroscopy. This discovery stands in sharp contrast to other glass-forming liquids. In this study, we conducted neural network force field driven molecular dynamic simulations of ZnCl2. We found a non-monotonic temperature dependence of β from liquid to supercooled liquid temperatures. Further structural decomposition and dynamic analysis suggest that this unusual dynamic behavior is a result of the competition between the decrease in the diversity of tetrahedra motifs (structural heterogeneity) and the increase in glassy dynamic heterogeneity. This result may contribute to new understandings of the structural relaxation of other network liquids.

Phonon Transport in Defect-Laden Bilayer Janus PtSTe Studied Using Neural-Network Force Fields.

We explore the phonon transport properties of defect-laden bilayer PtSTe using equilibrium molecular dynamics simulations based on a neural-network force field. Defects prove very efficient at depressing the thermal conductivity of the structure, and flower defects have a particularly powerful effect, comparable to that of double vacancies. Furthermore, the conductivity of the structure with flower defects exhibits an unusual temperature dependence due to structural instability at high temperatures. We look into the distortion to normal modes around the defect by means of the projected phonon density of states and find diverse phenomena including localized modes and blue shifts.

Enhanced magnetic anisotropy and its thermal stability in obliquely deposited Co-Film on the nanopatterned substrate

The deliberate manipulation of magnetic anisotropy through controlled adjustments to surface and interface morphology has become important due to its potential applications in spintronics and magnetic memory devices. In the present work, oblique angle deposition (OAD) at 65° to the surface normal on a rippled substrate, keeping nanopatterns on the SiO2 substrate perpendicular to the OAD projection, has been used to induce in-plane uniaxial magnetic anisotropy (UMA) and its thermal stability in cobalt (Co) thin film. Prior to film preparation, the patterned substrate of wavelength 68 ± 4 nm and amplitude 3.4 ± 0.2 nm was prepared separately using a low-energy ion beam erosion (IBE) process. Grazing incidence small-angle X-ray scattering (GISAXS) and magneto-optical Kerr effect (MOKE) techniques have been used for film characterization. While GISAXS provided information about film structure and morphology, MOKE provided information about magnetic properties, thus making it possible to correlate the temperature-dependent evolution of morphology with that of UMA in the film. A clear anisotropy in the growth of Co film is found to result in strong UMA. Unlike previous studies, which typically observe a reduction in UMA strength with thermal annealing, the present work demonstrates a 31 % increase in UMA strength after annealing up to 200 °C, underscoring the importance of oblique angle deposition on nano-rippled substrates for achieving high UMA and ensuring its thermal stability up to moderate temperatures. The appearance of large UMA and its unusual temperature dependence is understood in terms of the shadowing effects and column coalescence, resulting in more robust shape anisotropy. This work provides insights into morphological anisotropy, elucidating the interplay of shadowing effects, shape anisotropy, and dipolar interactions within interacting column and ripple structures. This method gives rise to morphology-induced anisotropy, which can also be applied to other ferromagnetic films to enhance the magnetic anisotropy and ensure thermal stability.

The Photosalient Effect and Thermochromic Luminescence Based on o‐Carborane‐Assisted π‐Stacking in the Crystalline State

AbstractHerein, we report the unique multiple‐stimuli responsiveness of anthracene‐tethered o‐carborane derivatives. We designed and synthesized anthracene derivatives with different substitution positions and numbers of the o‐carborane units. Two compounds had characteristic crystal structures involving the columnar π‐stacking structures of the anthracene units. From the analysis of crystalline‐state structure–property relationships, it was revealed that the crystals exhibited the photosalient effect accompanied by photochemical [4+4] cycloaddition reactions and temperature‐dependent photophysical dual‐emission properties including excimer emission of anthracene. Those properties were considered as non‐radiative and radiative deactivation pathways through the excimer formation in the excited state and the formation of excimer species was facilitated by the π‐stacking structure of anthracene units. Moreover, we found unusual temperature dependency on the occurrence of the photosalient effect. According to the data from variable temperature X‐ray crystallography, a strong correlation between lattice shrinkage and strain accumulation is suggested.

The Photosalient Effect and Thermochromic Luminescence Based on o-Carborane-Assisted π-Stacking in the Crystalline State.

Herein, we report the unique multiple-stimuli responsiveness of anthracene-tethered o-carborane derivatives. We designed and synthesized anthracene derivatives with different substitution positions and numbers of the o-carborane units. Two compounds had characteristic crystal structures involving the columnar π-stacking structures of the anthracene units. From the analysis of crystalline-state structure-property relationships, it was revealed that the crystals exhibited the photosalient effect accompanied by photochemical [4+4] cycloaddition reactions and temperature-dependent photophysical dual-emission properties including excimer emission of anthracene. Those properties were considered as non-radiative and radiative deactivation pathways through the excimer formation in the excited state and the formation of excimer species was facilitated by the π-stacking structure of anthracene units. Moreover, we found unusual temperature dependency on the occurrence of the photosalient effect. According to the data from variable temperature X-ray crystallography, a strong correlation between lattice shrinkage and strain accumulation is suggested.

Experimental nuclear quadrupole resonance and computational study of the structurally refined topological semimetal TaSb2

The local electric field gradients and magnetic dynamics of TaSb2 have been studied using Sb121, Sb123, and Ta181 nuclear quadrupole resonance (NQR) with density functional theory (DFT) calculations using XRD-determined crystal structures. By measuring all structurally expected 13 NQR lines, the nuclear quadrupole coupling constant (νQ) and asymmetric parameter (η) for Ta, Sb(1), and Sb(2) sites were obtained. These values are all in good agreement with the presented DFT calculations. Principal axes of the electric field gradients was determined for a single-crystal sample by measuring the angular dependencies of NMR frequency under a weak magnetic field. The unusual temperature dependence of η(T) of Sb(2) hints at the suppressed thermal expansion along the a axis. Spin-lattice relaxation rate (1/T1T) measurements reveal an activated-type behavior and an upturn below 30 K. Neither the low-temperature upturn nor the high-temperature activation-type behaviors are reproduced by the calculated 1/T1T based on the calculated density of states (DOS). On the other hand, the agreement between the calculated DOS and specific heat measurements indicates that the band renormalization is small. This fact indicates that TaSb2 deviates from the simple semimetal scenario, and magnetic excitations are not captured by Fermi liquid theory. Published by the American Physical Society 2024

Evidence of compensated semimetal with electronic correlations at charge neutrality of twisted double bilayer graphene

Recently, magic-angle twisted bilayer graphene (MATBLG) has emerged with various interaction-driven novel quantum phases at the commensurate fillings of the moiré superlattice, while the charge neutrality point (CNP) remains mostly a trivial insulator. Here, we show an emerging phase of compensated semimetallicity at the CNP of twisted double bilayer graphene (TDBLG), a close cousin of MATBLG, with signatures of electronic correlation. Using electrical and thermal transport, we find two orders of magnitude enhancement of the thermopower at magnetic fields much smaller than the extreme quantum limit, accompanied by large magnetoresistance ( ~ 2500%) at CNP, providing strong experimental evidence of compensated semimetallicity at CNP of TDBLG. Moreover, at low temperatures, we observe unusual sublinear temperature dependence of resistance. A recent theory1 predicts the formation of an excitonic metal near CNP, where small electron and hole pockets co-exist. We understand this sublinear temperature dependence in terms of critical fluctuations in this theory.

Anisotropic microwave response in Cr1∕3TaS2 hosting chiral magnetic soliton

Chromium-intercalated hexagonal Cr1∕3TaS2 possesses exotic properties, such as high-temperature magnetic soliton, crossover of critical behavior, and nontrivial magnetism. In this study, we employ the electron spin resonance (ESR) technique to modulate and study the chiral magnetic soliton lattice (CSL) in Cr1∕3TaS2 using microwave at X-band. The experimental results show that Cr1∕3TaS2 has a particularly strong microwave response when H⊥c but very weak feedback when H//c, revealing an anisotropic microwave response. When H⊥c, the resonance peak at lower fields results from the surface barrier induced by the competition between Dzyaloshinsky–Moriya interaction, Zeeman energy, and exchange energy. The dominant resonance is caused by the ferromagnetic mode with the twisted region as the boundary condition, which transforms into a paramagnetic resonance above the phase transition temperature (TC). Furthermore, an unusual temperature dependence of ESR spectra is revealed. The crystalline electric field (CEF) excitation owing to large strong spin–orbit coupling results in the widening of the ESR linewidth above TC. Furthermore, an abrupt shift in the resonance field Hr2 and ESR linewidth ΔHPP2 is observed around TC, which is attributed to a sudden change in spin-exchange interactions and magnetic anisotropy around TC, as Cr1∕3TaS2 was previously observed for spin interaction transition from strong anisotropic 3D-Ising type to isotropic 3D-Heisenberg magnetic interaction below TC. This work demonstrates that the ESR can detect the CSL state and investigate materials with nontrivial magnetism.

Intrinsically Low Thermal Conductivity in the Most Lithium-Rich Binary Stannide Crystalline Li5Sn.

Using ab initio lattice dynamics and a unified heat transport theory, we compute the lattice thermal conductivity (κL) of Li5Sn, a newly synthesized crystalline material for Li-ion batteries. The weak bonding in the Li-rich environment leads to significant softening of the optical phonon modes, temperature-induced hardening, and strong anharmonicity. This complexity is captured in the particle-like and glass-like components of κL by accounting for the temperature-dependent interatomic force constants acting on the renormalized phonon frequencies and three- and four-phonon scatterings contributing to the phonon lifetime. We predict very low room-temperature κL values of 0.857, 0.599, and 0.961 W/mK for the experimental Cmcm phase and 0.996, 0.908, and 1.385 W/mK for the theoretically predicted Immm phase along the main crystallographic directions. Both phases display complex crystal behavior with glass-like transport exceeding 20% above room-temperature and an unusual κL temperature dependence. Our results can be used to inform system-level thermal models of Li-ion batteries.

Quantum geometry induced anapole superconductivity

Anapole superconductivity recently proposed for multiband superconductors [S. Kanasugi and Y. Yanase, Commun. Phys. 5, 39 (2022)] is a key feature of time-reversal ($\mathcal{T}$) symmetry broken polar superconductors. The anapole moment was shown to arise from the asymmetric Bogoliubov spectrum, which induces finite center of mass momenta of Cooper pairs at the zero magnetic field. In this paper, we show an alternative mechanism of anapole superconductivity: the quantum geometry induces the anapole moment when the interband pairing and Berry connection are finite. Thus, the anapole superconductivity is a ubiquitous feature of $\mathcal{T}$-broken multiband polar superconductors. Applying the theory to a minimal model of ${\mathrm{UTe}}_{2}$, we demonstrate the quantum geometry induced anapole superconductivity. Furthermore, we show the Bogoliubov Fermi surfaces (BFS) in an anapole superconducting state and predict an unusual temperature dependence of BFS due to the quantum geometry. Experimental verification of these phenomena may clarify the superconducting state in ${\mathrm{UTe}}_{2}$ and reveal the ubiquitous importance of quantum geometry in exotic superconductors.

Suppression of high-temperature thermal conductivity due to electron-lattice coupling in PrAlO3, Tb2Ti2O7, and Dy3Al5O12

Thermal conductivities (κ) above 300 K are presented for a series of RAlO3 perovskites, R 2Ti2O7 pyrochlores, and R 3Al5O12 garnets, where R is a rare earth. We find unusual temperature dependence and suppression of κ in PrAlO3, Tb2Ti2O7, and Dy3Al5O12, which arise from interactions between the lattice phonons and electronic energy levels of R ions. These results indicate that proper consideration of electron-lattice coupling is necessary in assessing the high-temperature κ of R-based oxides, which are widely being examined for applications to thermal barrier coatings.

Atomic Displacements Enabling the Observation of the Anomalous Hall Effect in a Non-Collinear Antiferromagnet.

Antiferromagnets with non-collinear spin structures display various properties that make them attractive for spintronic devices. Some of the most interesting examples are an anomalous Hall effect despite negligible magnetization and a spin Hall effect with unusual spin polarization directions. However, these effects can only be observed when the sample is set predominantly into a single antiferromagnetic domain state. This can only be achieved when the compensated spin structure is perturbed and displays weak moments due to spin canting that allows for external domain control. In thin films of cubic non-collinear antiferromagnets, this imbalance waspreviously assumed to require tetragonal distortions induced by substrate strain. Here weshow that in Mn3 SnN and Mn3 GaN, spin canting is due to structural symmetry lowering induced by large displacements of the magnetic manganese atoms away from high symmetry positions. These displacements remain hidden in X-ray diffraction when only probing the lattice metric and require measurement of a large set of scattering vectors to resolve the local atomic positions. In Mn3 SnN, the induced net moments enable the observation of the anomalous Hall effect with an unusual temperature dependence, which weconjecture results from a bulk-like temperature-dependent coherent spin rotation within the Kagomeplane. This article is protected by copyright. All rights reserved.

Interference of excitons and surface plasmons in the optical absorption spectra of monolayer and bilayer graphene

By using spectroscopy ellipsometry, we investigated the optical absorption spectra of monolayer and bilayer graphene in the deep-ultraviolet region up to 6.42 eV as a function of temperature. The optical absorption spectra of monolayer and bilayer graphene can be fitted by two Breit-Wigner-Fano (BWF) spectral functions, in which each BWF is originated by the interference of discrete excitonic spectra and continuous surface plasmon spectra. Each BWF peak shows narrower linewidth and larger peak intensity with increasing temperature. The unusual temperature dependence of the BWF peaks is understood by a shorter lifetime of the surface plasmon at a higher temperature, which gives a smaller BWF asymmetric parameter. The optical absorption by the surface plasmon is usually observed only at the surface of the three-dimensional crystal or two-dimensional material. The contribution of the surface plasmon becomes relatively larger in the case of monolayer or bilayer graphene than that of single-crystal graphite because of the two-dimensional nature of electrons. The observed optical absorption spectra are confirmed by calculating the complex dielectric function using the first-principles calculations.

Unusual Temperature Dependence of Water Sorption in Semicrystalline Hydrogels.

Water vapor sorption is a ubiquitous phenomenon in nature and plays an important role in various applications, including humidity regulation, energy storage, thermal management, and water harvesting. In particular, capturing moisture at elevated temperatures is highly desirable to prevent dehydration and to enlarge the tunability of water uptake. However, owing to the thermodynamic limit of conventional materials, sorbents inevitably tend to capture less water vapor at higher temperatures, impeding their broad applications. Here, an inverse temperature dependence of water sorption in poly(ethylene glycol) (PEG) hydrogels, where their water uptake can be doubled with increasing temperature from 25 to 50°C, is reported. With mechanistic modeling of water-polymer interactions, this unusual water sorption is attributed to the first-order phase transformation of PEG structures, and the key parameters for a more generalized strategy in materials development are identified. This work elucidates a new regime of water sorption with an unusual temperature dependence, enabling a promising engineering space for harnessing moisture and heat.

Investigation of Dynamic Behavior of Confined Ionic Liquid [BMIM]+[TCM]- in Silica Material SBA-15 Using NMR.

The molecular dynamics of 1-butyl-3-methyl imidazolium tricyanomethanide ionic liquid [BMIM]+[TCM]- confined in SBA-15 mesoporous silica were examined using 1H NMR spin-lattice (T1) relaxation and diffusion measurements. An extensive temperature range (100 K-400 K) was considered in order to study both the liquid and glassy states. The hydrogen dynamics in the two states and the self-diffusion coefficients of the cation [BMIM]+ above the glass transition temperature were extracted from the experimental data. The results were then compared to the corresponding bulk substance. The effects of confinement on the dynamic properties of the ionic liquid clearly manifest themselves in both temperature regimes. In the high-temperature liquid state, the mobility of the confined cations reduces significantly compared to the bulk; interestingly, confinement drives the ionic liquid to the glassy state at a higher temperature Tg than the bulk ionic liquid, whereas an unusual T1 temperature dependence is observed in the high-temperature regime, assigned to the interaction of the ionic liquid with the silica-OH species.

Theoretical analysis of anisotropic upper critical field of superconductivity in nodal-line semimetals

We study the properties of the upper critical field of superconductivity in nodal-line semimetals in a continuous model, which has a nodal line on the ${k}_{z}=0$ plane. Using the semiclassical Green's function method, we calculate the upper critical field for the two limiting cases: the dirty limit with many impurities and the clean limit with few impurities. The results show the large anisotropy of the magnitude of the upper critical field and the unusual temperature dependence. The obtained results are compared with recent experimental data of ${\mathrm{PbTaSe}}_{2}$.

Nematic fluctuations in an orbital selective superconductor Fe1+yTe1−xSex

Fe1+yTe1−xSex is characterized by its complex magnetic phase diagram and highly orbital-dependent band renormalization. Despite this, the behavior of nematicity and nematic fluctuations, especially for high tellurium concentrations, remains largely unknown. Here we present a study of both B1g and B2g nematic fluctuations in Fe1+yTe1−xSex (0 ≤ x ≤ 0.53) using the technique of elastoresistivity measurement. We discovered that the nematic fluctuations in two symmetry channels are closely linked to the corresponding spin fluctuations, confirming the intertwined nature of these two degrees of freedom. We also revealed an unusual temperature dependence of the nematic susceptibility, which we attributed to a loss of coherence of the dxy orbital. Our results highlight the importance of orbital differentiation on the nematic properties of iron-based materials.