Search Results (29)

Electromagnetic waves propagating in a layered superconductor with arbitrary momentum, with respect to the main crystallographic directions, exhibit an unavoidable mixing between longitudinal and transverse degrees of freedom. Here we show that this basic physical mechanism explains the emergence of a well-defined absorption peak in the in-plane optical conductivity when light propagates at small tilting angles relative to the stacking direction in layered cuprates. More specifically, we show that this peak, often interpreted as a spurious leakage of the c-axis Josephson plasmon, is instead a signature of the true longitudinal plasma mode occurring at larger momenta. By combining a classical approach based on Maxwell’s equations with a full quantum derivation of the plasma modes based on modeling the superconducting phase degrees of freedom, we provide an analytical expression for the absorption peak as a function of the tilting angle and light polarization. We suggest that an all-optical measurement in tilted geometry can be used as an alternative way to access plasma-wave dispersion, usually measured by means of large-momenta scattering techniques like resonant inelastic X-ray scattering (RIXS) or electron energy loss spectroscopy (EELS). Full article

This paper reviews recent inelastic X-ray scattering investigations of simple inhomogeneous materials, such as nanoparticle suspensions in liquids. All studies reported emphasize the ability of immersed nanoparticles to dampen or attenuate acoustic waves through the hosting medium, the effect becoming even more pronounced upon freezing. Additionally, the results show that suspended nanoparticles can cause the onset of non-acoustic modes in the system. Also, the crucial role of Bayesian analysis in guiding spectral line shape modeling and interpretation is discussed. In summary, the presented results demonstrate that the simple inclusion of a sparse amount of nanoparticles profoundly influences sound propagation through a medium. This finding can inspire new avenues in the emerging field of terahertz acoustic steering and manipulation. Full article

This article experimentally investigates the inception of an innovative hard X-ray photon energy attenuation layer (PAL) to advance high-energy X-ray detection (20–50 keV). A bi-layer design with a thin film high-Z PAL on the top and Si image sensor on the bottom has previously demon-strated quantum yield enhancement via computational methods by the principle of photon energy down conversion (PEDC), where high-energy X-ray photon energies are attenuated via inelastic scattering down to ≤10 keV, which is suitable for efficient photoelectric absorption by Si. Quantum yield enhancement has been experimentally confirmed via a preliminary demonstration using PAL-integrated Si-based CMOS image sensors (Si CIS). Furthermore, substituting the high-Z PAL with a lower-Z material—Sn—and alternatively coupling it with a conventional scintillator ma-terial—Lutetium-yttrium oxyorthosilicate (LYSO)—have been compared to demonstrate the most prominent efficacy of monolithic integration of high-Z PAL on Si CIS to detect hard X-rays, paving the way for next-generation high-energy X-ray detection methods. Full article

X-ray photoelectron emission spectra of thermally reduced graphene oxide samples and carbon nanotubes (CNTs) with various oxidation degrees are presented in this paper. A method for the reconstruction of differential electron inelastic scattering cross sections from the energy loss spectra of photoelectrons is described and discussed. The analysis of the part of the characteristic photoelectron energy loss spectrum adjacent to the C1 peak indicated a considerable influence of the thermal reduction of graphene oxide on the electron properties of the samples obtained. On the contrary, the oxidation of CNTs by refluxing in a concentrated HNO₃ solution does not change the free electron excitation spectrum. Full article

As a contribution to the ongoing effort toward high-frequency sound manipulation in composite materials, we use Inelastic X-ray Scattering to probe the phonon spectrum of ice, either in a pure form or with a sparse amount of nanoparticles embedded in it. The study aims at elucidating the ability of nanocolloids to condition the collective atomic vibrations of the surrounding environment. We observe that a nanoparticle concentration of about 1 % in volume is sufficient to visibly affect the phonon spectrum of the icy substrate, mainly canceling its optical modes and adding nanoparticle phonon excitations to it. We highlight this phenomenon thanks to the lineshape modeling based on a Bayesian inference, which enables us to capture the finest detail of the scattering signal. The results of this study can empower new routes toward the shaping of sound propagation in materials through the control of their structural heterogeneity. Full article

The discovery of high-$T_c$ superconductivity in cuprates in 1986 moved strongly correlated systems from exotic worlds interesting only for pure theorists to the focus of solid-state research. In recent decades, the majority of hot topics in condensed matter physics (high-$T_c$ superconductivity, colossal magnetoresistance, multiferroicity, ferromagnetism in diluted magnetic semiconductors, etc.) have been related to strongly correlated transition metal compounds. The highly successful electronic structure calculations based on density functional theory lose their predictive power when applied to such compounds. It is necessary to go beyond the mean field approximation and use the many-body theory. The methods and models that were developed for the description of strongly correlated systems are reviewed together with the examples of response function calculations that are needed for the interpretation of experimental information (inelastic neutron scattering, optical conductivity, resonant inelastic X-ray scattering, electron energy loss spectroscopy, angle-resolved photoemission, electron spin resonance, and magnetic and magnetoelectric properties). The peculiarities of (quasi-) 0-, 1-, 2-, and 3- dimensional systems are discussed. Full article

The Museo Egizio’s collection contains 200 precious and unique leather artifacts belonging to different historical periods. The materials used during the tanning and curing procedures affect the chemical and elemental composition of the surface of the samples as well as their preservation status, specifically through the hydration level within the bulk. Here we provide an experimental characterization of a series of samples from Museo Egizio that document an extensive denaturation phenomenon (gelatinization), by combining non-destructive techniques including surface probes (X-ray fluorescence, Raman scattering, and scanning electron microscopy enhanced by X-ray energy spectroscopy) and neutron-based bulk techniques (inelastic and deep-inelastic neutron scattering). Results show partial dehydration of the samples in the bulk, affecting the morphology of their surface, the presence of potassium alum, and iron oxides, as well as phosphates and hydroxides related to the tanning and curing procedures. Finally, we briefly discuss the need for a versatile and adaptable software package that is capable of combining quantitative analyses with complementary techniques including morphological, elemental, and chemical composition. Full article

One of the grand challenges of new generation Condensed Matter physicists is the development of novel devices enabling the control of sound propagation at terahertz frequency. Indeed, phonon excitations in this frequency window are the leading conveyor of heat transfer in insulators. Their manipulation is thus critical to implementing heat management based on the structural design. To explore the possibility of controlling the damping of sound waves, we used high spectral contrast Inelastic X-ray Scattering (IXS) to comparatively study terahertz acoustic damping in a dilute suspension of 50 nm nanospheres in glycerol and on pure glycerol. Bayesian inference-based modeling of measured spectra indicates that, at sufficiently large distances, the spectral contribution of collective modes in the glycerol suspension becomes barely detectable due to the enhanced damping, the weakening, and the slight softening of the dominant acoustic mode. Full article

Ternary potassium-iron sulfide, KFeS₂, belongs to the family of highly anisotropic quasi-one-dimensional antiferromagnets with unusual “anti-Curie–Weiss” susceptibility, quasi-linearly growing with a rising temperature up to 700 K, an almost vanishing magnetic contribution to the specific heat, drastically reduced magnetic moment, etc. While some of the measurements can be satisfactorily described, the deficiency of the entropy changes upon the magnetic transition and the spin state of the iron ion remains a challenge for the further understanding of magnetism. In this work, high-quality single-crystalline samples of KFeS₂ were grown by the Bridgman method, and their stoichiometry, crystal structure, and absence of alien magnetic phases were checked, utilizing wave-length dispersive X-ray electron-probe microanalysis, powder X-ray diffraction, and ⁵⁷Fe Mössbauer spectroscopy, respectively. An ab initio approach was developed to calculate the thermodynamic properties of KFeS₂. The element-specific phonon modes and their density of states (PDOS) were calculated applying the density functional theory in the DFT + U version, which explicitly takes into account the on-site Coulomb repulsion U of electrons and their exchange interaction J. The necessary calibration of the frequency scale was carried out by comparison with the experimental iron PDOS derived from the inelastic nuclear scattering experiment. The infrared absorption measurements confirmed the presence of two high-frequency peaks consistent with the calculated PDOS. The calibrated PDOS allowed the calculation of the lattice contribution to the specific heat of KFeS₂ by direct summation over the phonon modes without approximations and adjustable parameters. The temperature-dependent magnetic specific heat evaluated by subtraction of the calculated phonon contribution from the experimental specific heat provides a lower boundary for estimating the reduced spin state of the iron ion. Full article

The question of the microscopic origin of the M-superstructure and additional satellite peaks in the Zr-rich lead zirconate-titanate is discussed for nearly 50 years. Clear contradiction between the selection rules of the critical scattering and the superstructure was found preventing unambiguous attributing of the observed superstructure either to the rotation of the oxygen octahedra or to the antiparallel displacements of the lead cations. Detailed analysis of the satellite pattern explained it as the result of the incommensurate phase transition rather than antiphase domains. Critical dynamics is the key point for the formulated problems. Recently, the oxygen tilt soft mode in the PbZr${}_{0.976}$Ti${}_{0.024}$O${}_3$ (PZT2.4) was found. But this does not resolve the extinction rules contradiction. The results of the inelastic X-ray scattering study of the phonon spectra of PZT2.4 around M-point are reported. Strong coupling between the lead and oxygen modes resulting in mode anticrossing and creation of the wide flat part in the lowest phonon dispersion curves is identified. This flat part corresponds to the mixture of the displacements of the lead and oxygen ions and can be an explanation of the extinction rules contradiction. Moreover, a flat dispersion surface is a typical prerequisite for the incommensurate phase transition. Full article

Because of its sensitivity to the instantaneous structure factor, S(Q,t = 0), Extended X-ray Absorption Fine Structure (EXAFS) is a powerful tool for probing the dynamic structure of condensed matter systems in which the charge and lattice dynamics are coupled. When applied to hole-doped cuprate superconductors, EXAFS has revealed the presence of internal quantum tunneling polarons (IQTPs). An IQTP arises in EXAFS as a two-site distribution for certain Cu–O pairs, which is also duplicated in inelastic scattering but not observed in standard diffraction measurements. The Cu–Sr pair distribution has been found to be highly anharmonic and strongly correlated to both the IQTPs and to superconductivity, as, for example, in ${\mathrm{YSr}}_2{\mathrm{Cu}}_{2.75}{\mathrm{Mo}}_{0.25}{\mathrm{O}}_{7.54}$$(T_c=84$ K). In order to describe such nontrivial, anharmonic charge-lattice dynamics, we have proposed a model Hamiltonian for a prototype six-atom cluster, in which two Cu-apical-O IQTPs are charge-transfer bridged through Cu atoms by an O atom in the ${\mathrm{CuO}}_2$ plane and are anharmonically coupled via a Sr atom. By applying an exact diagonalization procedure to this cluster, we have verified that our model indeed produces an intricate interplay between charge and lattice dynamics. Then, by using the Kuramoto model for the synchronization of coupled quantum oscillators, we have found a first-order phase transition for the IQTPs into a synchronized, phase-locked phase. Most importantly, we have shown that this transition results specifically from the anharmonicity. Finally, we have provided a phase diagram showing the onset of the phase-locking of IQTPs as a function of the charge-lattice and anharmonic couplings in our model. We have found that the charge, initially confined to the apical oxygens, is partially pumped into the ${\mathrm{CuO}}_2$ plane in the synchronized phase, which suggests a possible connection between the synchronized dynamic structure and high-temperature superconductivity (HTSC) in doped cuprates. Full article

Biochar (BCR) was obtained from the pyrolysis of a palm-oil-empty fruit bunch at 773 K for 2 h and used as a catalyst for the hydrodeoxygenation (HDO) of guaiacol (GUA) as a bio-oil model compound. Brunauer–Emmet–Teller surface area analysis, NH₃ and CO₂-temperature-programmed desorption, scanning electron microscope–dispersive X-ray spectroscopy, CHN analysis and X-ray fluorescence spectroscopy suggested that macroporous and mesoporous structures were formed in BCR with a co-presence of hydrophilic and hydrophobic sites and acid–base behavior. A combination of infrared, Raman and inelastic neutron scattering (INS) was carried out to achieve a complete vibrational assignment of BCR. The CH–OH ratio in BCR is ~5, showing that the hydroxyl functional groups are a minority species. There was no evidence for any aromatic C–H stretch modes in the infrared, but they are clearly seen in the INS and are the majority species, with a ratio of sp³–CH:sp²–CH of 1:1.3. The hydrogen bound to sp²–C is largely present as isolated C–H bonds, rather than adjacent C–H bonds. The Raman spectrum shows the characteristic G band (ideal graphitic lattice) and three D bands (disordered graphitic lattice, amorphous carbon, and defective graphitic lattice) of sp² carbons. Adsorbed water in BCR is present as disordered layers on the surface rather than trapped in voids in the material and could be removed easily by drying prior to catalysis. Catalytic testing demonstrated that BCR was able to catalyze the HDO of GUA, yielding phenol and cresols as the major products. Phenol was produced both from the direct demethoxylation of GUA, as well as through the demethylation pathway via the formation of catechol as the intermediate followed by deoxygenation. Full article

The ortho-hydroxy aryl Schiff base 2-[(E)-(phenylimino)methyl]phenol and its deutero-derivative have been studied by the inelastic incoherent neutron scattering (IINS), infrared (IR) and Raman experimental methods, as well as by Density Functional Theory (DFT) and Density-Functional Perturbation Theory (DFPT) simulations. The assignments of vibrational modes within the 3500–50 cm⁻¹ spectral region made it possible to state that the strong hydrogen bond in the studied compound can be classified as the so-called quasi-aromatic bond. The isotopic substitution supplemented by the results of DFT calculations allowed us to identify vibrational bands associated with all five major hydrogen bond vibrations. Quasi-isostructural polymorphism of 2-[(E)-(phenylimino)methyl]phenol (SA) and 2-[(E)-(phenyl-D₅-imino)methyl]phenol (SA-C₆D₅) has been studied by powder X-ray diffraction in the 20–320 K temperature range. Full article

The new complex of N,N-Dimethylglycine (DMG) with chloranilic acid (CLA) was synthesized and examined for thermal, structural, and dynamical properties. The structure of the reaction product between DMG and CLA was investigated in a deuterated dimethyl sulfoxide (DMSO-d6) solution and in the solid state by Nuclear Magnetic Resonance (NMR) (Cross Polarization Magic Angle Spinning-CPMAS NMR). The formation of the 1:1 complex of CLA and DMG in the DMSO solution was also confirmed by diffusion measurement. X-ray single crystal diffraction results revealed that the N,N-dimethylglycine–chloranilic acid (DMG⁺–CLA⁻) complex crystallizes in the centrosymmetric triclinic P-1 space group. The X-ray diffraction and NMR spectroscopy show the presence of the protonated form of N,N-dimethylglycine and the deprotonated form of chloranilic acid molecules. The vibrational properties of the co-crystal were investigated by the use of neutron (INS), infrared (IR), and Raman (RS) spectroscopies, as well as the density functional theory (DFT) with periodic boundary conditions. From the band shape analysis of the N–CH₃ bending vibration, we can conclude that the CH₃ groups perform fast (τ_R ≈ 10⁻¹¹ to 10^‒13 s) reorientational motions down to a temperature of 140 K, with activation energy at ca. 6.7 kJ mol⁻¹. X-ray diffraction and IR investigations confirm the presence of a strong N⁺–H···O⁻ hydrogen bond in the studied co-crystal. Full article

Conformational and polymorphic states in the nitro-derivative of o-hydroxy acetophenone have been studied by experimental and theoretical methods. The potential energy curves for the rotation of the nitro group and isomerization of the hydroxyl group have been calculated by density functional theory (DFT) to estimate the barriers of the conformational changes. Two polymorphic forms of the studied compound were obtained by the slow and fast evaporation of polar and non-polar solutions, respectively. Both of the polymorphs were investigated by Infrared-Red (IR) and Raman spectroscopy, Incoherent Inelastic Neutron Scattering (IINS), X-ray diffraction, nuclear quadrupole resonance spectroscopy (NQR), differential scanning calorimetry (DSC) and density functional theory (DFT) methods. In one of the polymorphs, the existence of a phase transition was shown. The position of the nitro group and its impact on the crystal cell of the studied compound were analyzed. The conformational equilibrium determined by the reorientation of the hydroxyl group was observed under argon matrix isolation. An analysis of vibrational spectra was achieved for the interpretation of conformational equilibrium. The infrared spectra were measured in a wide temperature range to reveal the spectral bands that were the most sensitive to the phase transition and conformational equilibrium. The results showed the interrelations between intramolecular processes and macroscopic phenomena in the studied compound. Full article