High-energy Modes Research Articles

Neutron Spectroscopy Evidence on the Dual Nature of Magnetic Excitations in a van der Waals Metallic Ferromagnet Fe2.72GeTe2

In the local or itinerant extreme, magnetic excitations can be described by the Heisenberg model which treats electron spins as localized moments, or by the itinerant-electron model where the exchange interaction between electrons leads to unequal numbers of electrons with up and down spins. However, it has been elusive when both local moments and itinerant electrons are present in the intermediate range. Using inelastic neutron scattering, we provide direct spectroscopic evidence on the coexistence of and interplay between local moments and itinerant electrons in a van der Waals metallic ferromagnet Fe$_{2.72}$GeTe$_{2}$, which can sustain tunable room-temperature ferromagnetism down to the monolayer limit. We find that there exist ferromagnetic spin-wave excitations dispersing from the zone center at low energies resulting from local moments, and a column-like broad continuum at the zone boundary at high energies up to over 100 meV resulting from itinerant electrons. Unlike the two-dimensional crystal structure, the low-energy mode exhibits a three-dimensional nature, and the high-energy mode also has an out-of-plane dependence. Both modes persist well above the Curie temperature of 160 K. Our neutron spectroscopic data reveal that the low-energy spin waves at 100 K are more coherent than those at 4 K, which is evidence of the weakening of the Kondo screening at high temperatures. These results unambiguously demonstrate the coexistence of local moments and itinerant electrons, and the Kondo effect between these two components in Fe$_{2.72}$GeTe$_{2}$. Such behaviors are generally expected in heavy-fermion systems with heavy $f$ electrons but rarely clearly observed in materials with light $d$ electrons. These findings shed light on the understanding of magnetism in transition-metal compounds.

Dual spectroscopic detection of THz energy modes of critical chemical compounds

Precise identification and sensing of organic and inorganic molecular systems are key factors in several applications in present industrial and scientific domains. While high energy modes, due to electronic interactions, are mostly impervious to the initial thermodynamic or chemical conditions, the low energy modes are sensitive to such alterations which makes them suitable for quality control purpose with sensitive spectral identification methods. Here we report for the first time, several low frequency peaks of specific nitrogen-based compounds and their derivatives, using the dual spectroscopic approach of Terahertz Time-Domain Spectroscopy (THz-TDS) and THz Raman Spectroscopy (THz-RS). Two different isomeric molecular systems have also been investigated to assess both the selectivity and specificity of low energy modes in their identification and spectral correlation in terms of molecular interactions. This information of low frequency modes can be utilized readily by pharmaceutical and agri-food industries, chemical engineering and crystal growth communities in identification, detection, quality control and industrial waste management.

Removal of the highest energy POD mode for optimal construction of subgrid-scale parameters in a SPIV-measured turbulent mixing layer flow

Large eddy simulation is based on decomposition of turbulent flow structures to large energy-containing scales and small subgrid-scale (SGS) structures. The present study analyzes the effect of removing high-energy modes of flow to find the optimal construction of SGS parameters using the a priori approach. The data belong to a shear layer flow measured by stereoscopic particle image velocimetry (SPIV). The proper orthogonal decomposition (POD) method is used to capture all energy modes of the acquired velocity field. The missing/erroneous data are reconstructed using the gappy POD method. Particularly, similarity and mixed models are used to evaluate the SGS parameters. The results of the mixed model are compared via the a priori approach, before and after removing the high-energy modes. For the present flow, it is found that removal of just the first POD mode (as a representative of the mean flow) leads to the best SGS reconstruction, and this results in one order of magnitude higher precision of the average SGS stresses.

Fractional and composite excitations of antiferromagnetic quantum spin trimer chains

Using quantum Monte Carlo, exact diagonalization, and perturbation theory, we study the spectrum of the S = 1/2 antiferromagnetic Heisenberg trimer chain by varying the ratio g = J2/J1 of the intertrimer and intratrimer coupling strengths. The doublet ground states of trimers form effective interacting S = 1/2 degrees of freedom described by a Heisenberg chain. Therefore, the conventional two-spinon continuum of width ∝ J1 when g = 1 evolves into to a similar continuum of width ∝ J2 when g → 0. The intermediate-energy and high-energy modes are termed doublons and quartons which fractionalize with increasing g to form the conventional spinon continuum. In particular, at g ≈ 0.716, the gap between the low-energy spinon branch and the high-energy band with mixed doublons, quartons, and spinons closes. These features should be observable in inelastic neutron scattering experiments if a quasi-one-dimensional quantum magnet with the linear trimer structure and J2 < J1 can be identified. Our results may open a window for exploring the high-energy fractional excitations.

Magnetization dynamics fingerprints of an excitonic condensate t2g4 magnet

The competition between spin-orbit coupling $\lambda$ and electron-electron interaction $U$ leads to a plethora of novel states of matter, extensively studied in the context of $t_{2g}^4$ and $t_{2g}^5$ materials, such as ruthenates and iridates. Excitonic magnets -- the antiferromagnetic state of bounded electron-hole pairs -- is a prominent example of phenomena driven by those competing energy scales. Interestingly, recent theoretical studies predicted that excitonic magnets can be found in the ground-state of spin-orbit-coupled $t_{2g}^4$ Hubbard models. Here, we present a detailed computational study of the magnetic excitations in that excitonic magnet, employing one-dimensional chains (via density matrix renormalization group) and small two-dimensional clusters (via Lanczos). Specifically, first we show that the low-energy spectrum is dominated by a dispersive (acoustic) magnonic mode, with extra features arising from the $\lambda=0$ state in the phase diagram. Second, and more importantly, we found a novel magnetic excitation forming a high-energy optical mode with the highest intensity at wavevector $q\to 0$. In the excitonic condensation regime at large $U$, we also have found a novel high-energy $\pi$-mode composed solely of orbital excitations. These unique fingerprints of the $t_{2g}^4$ excitonic magnet are important in the analysis of neutron and RIXS experiments.

Analysis of Grape Volatiles Using Atmospheric Pressure Ionization Gas Chromatography Mass Spectrometry-Based Metabolomics.

Analysis of volatile compounds in fruits and plants can be a challenging task as they present in a large amount with structural diversity and high aroma threshold, the information on molecular ion can be very useful for compound identification. Electron ionization gas-chromatography-mass spectrometry (EI-GC-MS) which is widely used for the analysis of plant volatiles has a certain limitation providing the limited capability to characterize novel metabolites in a complex biological matrix due to hard fragmentation level. Atmospheric pressure ionization using APGC source in combination with high-resolution time-of-flight mass spectrometry (TOF-MS) provides an excellent combination of GC with high-resolution mass spectrometry. The APGC-MS approach provides several advantages over the conventional EI and CI based GC-MS techniques in metabolomics studies due to highly reduced fragmentation, which preserves molecular ion, and accurate mass measurement by HRMS allows to deduce the elemental composition of the volatile compounds. Moreover, the use of MSE mode provides spectral similarity to EI in high-energy mode which can be used for the further confirmation of metabolite identity. We describe an APGC-MS-based untargeted metabolomics approach with a case study of grape volatile compounds and the development of a spectral library for metabolite identification.

Anomalous spin exciton with a magnetoroton minimum in a quantum Hall ferromagnet at a filling factor ν=2

In ZnO-based two-dimensional electron systems with strong Coulomb interaction, the anomalous spin-exciton branch is revealed. As probed by inelastic light scattering, in a ferromagnetic quantum-Hall state with the filling factor $\ensuremath{\nu}=2$, a spin exciton has a negative momentum dispersion with steepness dependent on the electron density. The negative dispersion of the spin exciton is associated with its interaction with higher-energy spin-flip modes that exist near $\ensuremath{\nu}=2$. Surprisingly, the anti-Stokes light scattering on spin excitons at ferromagnetic state $\ensuremath{\nu}=2$ is amplified by orders of magnitude, indicating the macroscopic accumulation of these excitations. The experimental findings are confirmed by the exact diagonalization method---these calculations show a magnetoroton minimum in the dispersion of spin excitons and also the attractive interaction between magnetoroton spin excitations.

High-energy ball milling and spark plasma sintering of molybdenum - lanthanum oxide (Mo-La2O3) and molybdenum – lanthanum zirconate (Mo-La2Zr2O7) composite powders

The current study is focused on the preparation of Mo-10 vol%La2O3 and Mo-10 vol% La2Zr2O7 composite powders via low- and high-energy ball milling approaches as potential candidates for near-future high-temperature structural applications. The mechanical milling parameters play a critical role on the final powder's microstructure. When using the high-energy milling mode (using 800 rpm, ball-to-powder ratio (BPR) 100: 6), the homogeneous powder agglomerates are formed with refined laminated microstructure and more uniform ceramic phase distribution in both Mo-La2O3 and Mo-La2Zr2O7 systems compared to the powders produced by means of the low-energy milling mode (using 350 rpm, BPR 100: 6), where inhomogeneous powder mixture with less embedding of ceramic phases into Mo agglomerates was obtained. This study also focuses on the evaluation of high-temperature phase and microstructural stability of the produced composite powders treated at the temperature of 1300 °C under the different gaseous environments, including ambient, inert and reducing atmospheres. The Mo-10 vol% La2Zr2O7 composite powder exhibited better thermal stability during the high-temperature exposure in all tested atmospheres in comparison with the Mo-La2O3 composite powder, since it revealed less intensive formation of the intermediate phases, such as lanthanum oxymolybdates. Therefore, the Mo-10 vol% La2Zr2O7 composite powder was used further for consolidation by means of spark plasma sintering at 1600 °C. The successful production of Mo-La2Zr2O7 composite with homogeneous distribution of ceramic phase, the grain size about of 5 μm, and hardness of 3.4 GPa was not reported so far.

Nonclassical Exciton Diffusion in Monolayer WSe_{2}.

We experimentally demonstrate time-resolved exciton propagation in a monolayer semiconductor at cryogenic temperatures. Monitoring phonon-assisted recombination of dark states, we find a highly unusual case of exciton diffusion. While at 5K the diffusivity is intrinsically limited by acoustic phonon scattering, we observe a pronounced decrease of the diffusion coefficient with increasing temperature, far below the activation threshold of higher-energy phonon modes. This behavior corresponds neither to well-known regimes of semiclassical free-particle transport nor to the thermally activated hopping in systems with strong localization. Its origin is discussed in the framework of both microscopic numerical and semiphenomenological analytical models illustrating the observed characteristics of nonclassical propagation. Challenging the established description of mobile excitons in monolayer semiconductors, these results open up avenues to study quantum transport phenomena for excitonic quasiparticles in atomically thin van der Waals materials and their heterostructures.

Prediction of a new zigzag shape Be2C monolayer as a photo-catalyst for water splitting: A first principles study

In this work, we theoretically predict a new 2D Zigzag-shape Beryllium Carbide (Be2C) Monolayer. The proposed Zigzag-shape Be2C monolayers, buckled with two adjacent quasi-planar rows of Be and C atoms connected to the middle Be plane by Be–C bonds and it is formed by tetraco-ordinate carbon and bi-coordinate Beryllium atoms. The newly designed 2D Be2C monolayer is a stable structure as confirmed by its high cohesive energy and positive phonon modes. Based on our electrical properties investigations, perfectly planar and a Zigzag-shape Be2C monolayer is a semiconductor material with moderate bandgaps of 2.42 eV calculated by hybrid functional level of theory (HSE06). Moreover, the effect of biaxial strains on the electric properties of the monolayer is studied and it was found that its electric properties can be effectively tuned by strain effects. According to HSE functional, the band gap increases by about 20% with 3% of compressive strain and decreases by 21% for the case of 3% tensile strain . Furthermore, the proposed 2D monolayer shows considerable interesting electrical properties suggest this monolayer semiconductor as a very good candidate for using in hydrogen production by water splitting process. • A new Zigzag-shape Be 2 C monolayer is theoretically predicted. • The Zigzag-shape Be 2 C monolayer shows good structural and kinetically stabilities. • The Zigzag-shape Be 2 C monolayer is a semiconductor with moderate bandgaps of 2.42 eV HSE06 theory. • The Zigzag-shape Be 2 C monolayer a very good candidate for using in water splitting applications.

Hierarchical excitations from correlated spin tetrahedra on the breathing pyrochlore lattice

The hierarchy of the coupling strengths in a physical system often engenders an effective model at low energies where the decoupled high-energy modes are integrated out. Here, using neutron scattering, we show that the spin excitations in the breathing pyrochlore lattice compound $\mathrm{Cu}\mathrm{In}{\mathrm{Cr}}_{4}{\mathrm{S}}_{8}$ are hierarchical and can be approximated by an effective model of correlated tetrahedra at low energies. At higher energies, intratetrahedron excitations together with strong magnon-phonon couplings are observed, which suggests the possible role of the lattice degree of freedom in stabilizing the spin tetrahedra. Our work illustrates the spin dynamics in $\mathrm{Cu}\mathrm{In}{\mathrm{Cr}}_{4}{\mathrm{S}}_{8}$ and demonstrates a general effective-cluster approach to understand the dynamics on the breathing-type lattices.

Strong anharmonicity in tin monosulfide evidenced by local distortion, high-energy optical phonons, and anharmonic potential

Recently, SnSe has been found to possess a remarkable thermoelectric performance. As an isostructural compound to SnSe, SnS contains a more environmentally compatible and earth abundant element, which enables SnS a promising thermoelectric material for commercial application. In this work, we have performed systematic studies of the crystal structures and the lattice vibrations by means of neutron total scattering, Raman scattering measurements, and first-principle calculations. A structural transition has been observed by both temperature dependent neutron diffraction and pressure dependent Raman scattering. The lattice anharmonicity has been revealed by the local distortion induced by the Sn $5{s}^{2}$ lone pair and is also evidenced from the temperature dependent atomic displacement parameter of the Sn atom. By separating the intrinsic anharmonicity and lattice thermal expansion effects, we found that the former plays the primary role in the softening of the Raman active modes. Such anharmonicity has also been observed experimentally by the linewidth broadening of the high-energy optical modes and confirmed by frozen phonon calculations. Furthermore, our frozen phonon calculation reveals the presence of the quartic anharmonicity potential of those high-energy optical modes vibrating along the $b$ axis. Our data will contribute to a better understanding of the thermal conduction in SnS, which will be beneficial for the enhancement of the thermoelectric performance of this material.

Evaluation of the Double Snap-Through Mechanism on the Wave Energy Converter\u2019s Performance

Lower efficiencies induce higher energy costs and pose a barrier to wave energy devices’ commercial applications. Therefore, the efficiency enhancement of wave energy converters has received much attention in recent decades. The reported research presents the double snap-through mechanism applied to a hemispheric point absorber type wave energy converter (WEC) to improve the energy absorption performance. The double snap-through mechanism comprises four oblique springs mounted in an X-configuration. This provides the WEC with different dynamic stability behaviors depending on the particular geometric and physical parameters employed. The efficiency of these different WEC behaviors (linear, bistable, and tristable) was initially evaluated under the action of regular waves. The results for bistable or tristable responses indicated significant improvements in the WEC’s energy capture efficiency. Furthermore, the WEC frequency bandwidth was shown to be significantly enlarged when the tristable mode was in operation. However, the corresponding tristable trajectory showed intra-well behavior in the middle potential well, which induced a more severe low-energy absorption when a small wave amplitude acted on the WEC compared to when the bistable WEC was employed. Nevertheless, positive effects were observed when appropriate initial conditions were imposed. The results also showed that for bistable or tristable responses, a suitable spring stiffness may cause the buoy to oscillate in high energy modes.

Entropy production for quasiadiabatic parameter changes dominated by hydrodynamics

A typical strategy of realizing an adiabatic change of a many-particle system is to vary parameters very slowly on a time scale $t_\text{r}$ much larger than intrinsic equilibration time scales. In the ideal case of adiabatic state preparation, $t_\text{r} \to \infty$, the entropy production vanishes. In systems with conservation laws, the approach to the adiabatic limit is hampered by hydrodynamic long-time tails, arising from the algebraically slow relaxation of hydrodynamic fluctuations. We argue that the entropy production $\Delta S$ of a diffusive system at finite temperature in one or two dimensions is governed by hydrodynamic modes resulting in $\Delta S \sim 1/\sqrt{t_\text{r}}$ in $d=1$ and $\Delta S \sim \ln(t_\text{r})/t_\text{r}$ in $d=2$. In higher dimensions, entropy production is instead dominated by other high-energy modes with $\Delta S \sim 1/t_\text{r}$. In order to verify the analytic prediction, we simulate the non-equilibrium dynamics of a classical two-component gas with point-like particles in one spatial dimension and examine the total entropy production as a function of $t_\text{r}$.

Unraveling the Orbital Physics in a Canonical Orbital System KCuF_{3}.

We explore the existence of the collective orbital excitations, orbitons, in the canonical orbital system KCuF_{3} using the Cu L_{3}-edge resonant inelastic x-ray scattering. We show that the nondispersive high-energy peaks result from the Cu^{2+} dd orbital excitations. These high-energy modes display good agreement with the abinitio quantum chemistry calculation, indicating that the dd excitations are highly localized. At the same time, the low-energy excitations present clear dispersion. They match extremely well with the two-spinon continuum following the comparison with Müller ansatz calculations. The localized dd excitations and the observation of the strongly dispersive magnetic excitations suggest that the orbiton dispersion is below the resolution detection limit. Our results can reconcile with the strong local Jahn-Teller effect in KCuF_{3}, which predominantly drives orbital ordering.

Many-Body Decay of the Gapped Lowest Excitation of a Bose-Einstein Condensate.

We study the decay mechanism of the gapped lowest-lying axial excitation of a quasipure atomic Bose-Einstein condensate confined in a cylindrical box trap. Owing to the absence of accessible lower-energy modes, or direct coupling to an external bath, this excitation is protected against one-body (linear) decay, and the damping mechanism is exclusively nonlinear. We develop a universal theoretical model that explains this fundamentally nonlinear damping as a process whereby two quanta of the gapped lowest excitation mode couple to a higher-energy mode, which subsequently decays into a continuum. We find quantitative agreement between our experiments and the predictions of this model. Finally, by strongly driving the system below its (lowest) resonant frequency, we observe third-harmonic generation, a hallmark of nonlinear behavior.

Non-linear Terahertz driving of plasma waves in layered cuprates

The hallmark of superconductivity is the rigidity of the quantum-mechanical phase of electrons, responsible for superfluid behavior and Meissner effect. The strength of the phase stiffness is set by the Josephson coupling, which is strongly anisotropic in layered cuprates. So far, THz light pulses have been used to achieve non-linear control of the out-of-plane Josephson plasma mode, whose frequency lies in the THz range. However, the high-energy in-plane plasma mode has been considered insensitive to THz pumping. Here, we show that THz driving of both low-frequency and high-frequency plasma waves is possible via a general two-plasmon excitation mechanism. The anisotropy of the Josephson couplings leads to markedly different thermal effects for the out-of-plane and in-plane response, linking in both cases the emergence of non-linear photonics across Tc to the superfluid stiffness. Our results show that THz light pulses represent a preferential knob to selectively drive phase excitations in unconventional superconductors.

Spin-wave resonance frequency in ferromagnetic thin film with the next nearest neighbor interaction

Linear spin-wave approximation and Green's function were used to study the dependence of spin wave resonance (SWR) frequency in a ferromagnetic film considering the external magnetic field, surface anisotropy, number of atomic layers, nearest and next nearest neighbor interaction. A systematic study of the SWR frequency as a function of external magnetic field, surface anisotropy, and next nearest neighbor interaction was performed. It demonstrates that the next nearest neighbor interaction affects strongly on the SWR frequencies of energetically higher modes, as well as the gap of resonance frequency between the highest and lowest energy modes is broaden as the next nearest neighbor interaction increasing. Moreover, we show that SWR frequencies at two higher energy modes are coincided when the surface anisotropy increases. Finally, as the thickness of film decreases, SWR frequency of the lowest energy mode is shifted to higher value. Thus, considering these effects in an opportune way, we are able to control the SWR frequency of the system.

Singlet Fission Dynamics in Tetracene Single Crystals Probed by Polarization-Dependent Two-Dimensional Electronic Spectroscopy.

The exact mechanism of endothermic singlet fission in crystalline polyacene remains to be clarified. It has been elusive whether the excess energy of vibrational hot states and the upper branch of Davydov splitting is important for the energy compensation. Here, we probe the excited-state specified singlet fission dynamics in tetracene single crystals by polarization-dependent two-dimensional electronic spectroscopy (2DES). While a major spectral transfer with a characteristic lifetime of 86 ps is observed to be largely independent of the excitation energy due to formation of the spatially separated triplet pairs (1(T···T)), the excitation-energy dependent subpicosecond dynamics show marked differences for different states probed, implying the possible involvement of a coherently formed triplet pair state (1(TT)). Analysis of coherent vibrational modes suggests the coupling to high energy modes may offset the energy difference between singlet and triplet pair states. Moreover, the beating map of the low frequency mode indicates a vibrational hot state violating the aggregation behavior of Davydov exciton, which can be explained as a resonance of the 1(TT) state. These results suggest that the coherent vibronic mixing between local excitation and triplet pair states is essential for the singlet fission dynamics in molecule aggregates.

High-Performance n-type SnSe Thermoelectric Polycrystal Prepared by Arc-Melting

Summary Tin selenide (SnSe) has notable thermoelectric properties, yet stable n-type polycrystalline SnSe is difficult to synthesize. Here, polycrystalline SnSe is easily prepared by arc-melting as robust pellets, with thermoelectric properties repeatably changing to negative Seebeck-coefficient above 580 K reaching a figure of merit ∼1.8 at 816 K. DC conductivity changes 4 orders of magnitude with temperature, whereas microwave conductivity increases only 4-fold, confirming the effects of oxidized grain boundaries. Effects of ambient oxygen exposure are probed by X-ray photoelectron spectroscopy. Neutron powder diffraction reveals 3% Sn deficiency. Inelastic neutron scattering shows phonon spectrum consistent with ab initio calculations and reported Raman spectra, but with higher-energy modes strongly softened at higher temperatures. We thereby provide insight on undoped n-type polycrystalline SnSe that reveals high-performance at high temperature, being a suitable peer material for p-type SnSe.