Spectra Of Crystals Research Articles

Raman scattering of omphacite at high pressure: Toward its possible application to elastic geothermobarometry

Abstract Due to their widespread occurrence in several geological settings, omphacite inclusions could be used for elastic Raman geothermobarometry. However, the Raman scattering of complex silicate minerals entrapped in a host depends on both the chemical composition and elastic strain developed during the metamorphic pathway, which makes the task very challenging. Here, as a very first step to probe the potential of omphacite to be used as a mineral inclusion in elastic geothermobarometry, we report the pressure dependence of the Raman spectra of omphacite crystals with the same composition, approximately Jd43Di57, but having different symmetry because of the existence (P2/n) or absence (C2/c) of chemical order at the six- and eight-coordinated cation sites. The experimental results are complemented by ab initio quantum mechanical simulations on fully ordered omphacite (Jd50Di50). We demonstrate that the position of the well-resolved Raman peak near 688 cm–1, arising from Si-O-Si bond bending, is very sensitive to pressure but independent of the state of chemical order, which makes it promising to be utilized in Raman geobarometry. The width of this peak varies with chemical order but not with pressure and therefore can be used to constrain the temperature of inclusion entrapment, because the chemical order is indicative of the closure temperature of the cation-exchange reaction. However, further detailed analyses on the compositional variation of the Raman spectra of omphacite is required before considering omphacite-in-garnet systems to be suitable for Raman elastic geothermobarometry.

Donepezil hydrochloride fingerprint spectral and formation mechanism analysis.

Donepezil hydrochloride is a widely used medication for treating Alzheimer's disease. This study utilized terahertz time-domain spectroscopy to analyze the fingerprint spectra of donepezil hydrochloride, identifying five characteristic absorption peaks at 1.65, 2.44, 2.56, 3.31, and 3.75THz. The vibrational spectrum of the donepezil hydrochloride crystal was further examined using solid-state density functional theory. Based on simulation calculations, the characteristic peaks were identified and analyzed in detail, focusing on long-range ordering and weak interaction networks. The results demonstrate that terahertz spectroscopy is an effective tool for studying intermolecular interactions in drug crystals.

Solvatochromism, electric dipole moments, optical properties and electronic structure of biphenylcarbonitrile liquid crystals

The UV–Vis. absorbance and fluorescence spectra of 4HC (4′-heptyl-4-biphenyl carbonitrile) and 4OB (4′-Octyl-4-biphenylcarbonitrile) liquid crystals were measured in 23 solvents with different polarities. As dependent on changing of solvents, while the change in absorbance spectrum of liquid crystals have less, change in fluorescence spectrum have more. Molecular interactions were quantitavely investigated by using Linear solvation energy relationships. Optical forbidden energy gap has been determined with using Tauc plot. The refractive index has been calculated with semi-empirical methods. The relationships between refractive index and Eg has been commented in n-hexane, acetic acid, water and 1,4-dioxane. The electric dipole moment has been calculated by using the Bilot-Kawski, Lippert-Mataga, Bakshiev, Kawski-Chamma-Viallet and Reichardt methods. Solvatochromic shifts showed to having large dipole moments of 4OB and 4HC LCs. Their molecular orbital energies, electric dipole moments, MEP, SAS, and reactivity properties of 4HC and 4OB LCs has been found by quantum chemical calculations. It was observed that the dipole moment of 4HC was higher than 4OB.

Enhanced emission and surface modification in ZnO treated with Ar, H, and O plasmas

Plasma treatment is a crucial technique for manipulating the optoelectronic properties of ZnO devices by modifying surface defects. The choice of plasma gas in the treatment process significantly influences these defects, as evidenced by the luminescence characteristics. In this paper, significant differences have been observed in the photoluminescence spectra of ZnO films and single crystals before and after treatment with three kinds of plasma gas. After Ar and H plasma treatment, the UV emission is significantly enhanced up to 1000 times, while the visible emission is suppressed. Conversely, after O plasma treatment, the UV emission remains unchanged, but the deep level emission exhibits a subtle transformation. Since the influence depth of plasma treatment is confined to the surface, all these alterations of typical luminescence are strongly dependent on surface-related defects, thereby challenging the previous interpretation that they originate from bulk defects. The modification effects of various plasmas on surfaces are confirmed from multiple perspectives, and the mechanisms behind the enhancement or suppression of luminescence are systematically analyzed. A comprehensive understanding of plasma treatment, along with precise control of surface defects, is crucial for optimizing the performance of ZnO devices.

One-Dimensional Photonic Crystals Comprising Two Different Types of Metamaterials for the Simple Detection of Fat Concentrations in Milk Samples.

In this study, we demonstrate the reflectance spectrum of one-dimensional photonic crystals comprising two different types of metamaterials. In this regard, the designed structure can act as a simple and efficient detector for fat concentrations in milk samples. Here, the hyperbolic and gyroidal metamaterials represent the two types of metamaterials that are stacked together to construct the candidate structure; meanwhile, the designed 1D PCs can be simply configured as [G(ED)m]S. Here, G refers to the gyroidal metamaterial layers in which Ag is designed in a gyroidal configuration form inside a hosting medium of TiO2. In contrast, (ED) defines a single unit cell of the hyperbolic metamaterials in which two layers of porous SiC (E) and Ag (D) are combined together. It is worth noting that our theoretical and simulation methodology is essentially based on the effective medium theory, characteristic matrix method, Drude model, Bruggeman's approximation, and Sellmeier formula. Accordingly, the numerical findings demonstrate the emergence of three resonant peaks at a specified wavelength between 0.8 μm and 3.5 μm. In this context, the first peak located at 1.025 μm represents the optimal one regarding the detection of fat concentrations in milk samples due to its low reflectivity and narrow full bandwidth. Accordingly, the candidate detector could provide a relatively high sensitivity of 3864 nm/RIU based on the optimal values of the different parameters. Finally, we believe that the proposed sensor may be more efficient compared to other counterparts in monitoring different concentrations of liquid, similar to fats in milk.

Features of the defect structure of a lithium-gradient nonlinear optical single crystal LiNbO3 and their manifestation in the Raman spectra

LiNbO3 crystal with a lithium composition gradient of Li/Nb = 0.8 wt%/cm (Li0.97..1.01Nb1.03..0.99O3) were obtained. A monotonic change in the edge of the UV absorption edge is observed when scanning the surface of the gradient crystal along the growth direction. Raman spectra from different areas of studied crystal were analyzed in a wide frequency range, which includes the region of fundamental vibrations of the crystal lattice (100–900 cm−1) and the region of overtone processes (900–3000 cm−1). A compositionally homogeneous, congruent LiNbO3 crystal was used as a comparison sample. It was found that in the spectra obtained from different parts of the gradient crystal, there is a significant scatter in the frequency values of the lines corresponding to the fundamental vibrations of the crystal lattice, but at the same time, the number of lines corresponding to the fundamental vibrations of the lattice for the gradient and compositionally homogeneous LiNbO3 crystals is the same. Moreover, in the spectrum of a gradient crystal in the region of overtone processes of fundamental vibrations, significantly more lines (35 lines) are observed than in the spectrum of compositionally homogeneous crystals (15 lines). The data obtained show that the state of the defect structure of compositionally homogeneous crystals and gradient LiNbO3 crystal is significantly different. The discovered differences between the defective structure of a gradient crystal and the defective structure of a compositionally homogeneous crystal may be the reason for compensation (damping) of distortions during nonlinear optical conversion of laser radiation by a gradient crystal due to the uneven temperature distribution along the length of the crystal. In compositionally homogeneous crystals, such temperature distortions significantly limit the efficiency of nonlinear optical conversion.

Piezo-optical properties and infrared spectra of Rb2SO4 crystals

The paper deals with the dispersion dependences of birefringence Δni(λ) of the mechanically free and uniaxially clamped Rb2SO4 crystal along different crystal-physical axes at room temperature. It was found that the crystal has an insignificant normal dispersion d(Δnx)/dλ χ ≤ 0, and uniaxial compressions σm do not change the character, but only the slope of the dependences Δni(λ). Uniaxial loads shift the position of the optical isotropic point both in the short-wavelength (σz) and in the long-wavelength part of the spectrum (σy). The spectral dependences of the combined piezo-optical coefficients πkmo(λ) were calculated and it was found that they have an insignificant dispersion dependence, and the absolute values of the piezo-optical coefficients π31o and π21o are equal to each other in the vicinity of the optical isotropic point at the light wavelength λ = 490 nm. The reflection spectra of Rb2SO4 crystals were measured in the infrared range at room temperature using FT-IR spectrometer and synchrotron radiation and the corresponding ab initio calculations of the phonon partial density of states and the dielectric function were performed.

The Crystal Chemistry of Boussingaultite, (NH4)2Mg(SO4)2·6H2O, and Its Derivatives in a Wide Temperature Range

The crystal structure, thermal behavior, and vibrational spectra of the anthropogenic analogue of boussingaultite, (NH4)2Mg(SO4)2·6H2O, and its dehydrated counterpart efremovite, (NH4)2Mg2(SO4)3, were studied in detail. The sample from the Chelyabinsk burning coal dumps has the composition of (NH4)1.92(Mg1.02Mn0.01Fe0.01)∑1.04(SO4)2·6H2O and crystallizes in the space group P21/a, with a = 9.3183(4), b = 12.6070(4), c = 6.2054(3) Å, β = 107.115(5)°, V = 696.70(5) Å3 (at 20 °C), Z = 2. The thermal evolution steps are as follows: boussingaultite (NH4)2Mg(SO4)2·6H2O (25–90 °C) → X-ray amorphous phase (100–150 °C) → efremovite (NH4)2Mg2(SO4)3 (160–340 °C) → MgSO4 Cmcm + Pbnm (340–580 °C) → MgSO4 Pbnm (580–700 °C). Thermal expansion is anisotropic, with the coefficients (×106 °C−1) α11 = 52(2), α22 = 68(2), α33 = –89(3), and αv = 31(3) at T = –123 °C; and α11 = 53(2), α22 = 67(2), α33 = 15(1), and αv = 136(3) at T = 60 °C. The maximal thermal expansion is along the b-axis and is due to straightening of corrugated pseudolayers (within the ab plane) of Mg(H2O)6 octahedra and SO4 tetrahedra with NH4 groups in the interlayer space. Vibrational spectroscopy outlines the general trend of dehydration and deammonization as the difference in the temperature intervals of these transformation steps allows separation of O–H and N–H vibrations in the process of dehydration by infrared and Raman spectroscopy. The intermediate partially dehydrated modification of boussingaultite was detected by in situ Raman spectroscopy at 110 °C that may correspond to ammonium leonite.

The infrared spectrum of the protic ionic liquid 1-methylimidazolium nitrate: An ab initio molecular dynamics simulation study

Complex features observed in the infrared (IR) spectrum of the protic ionic liquid 1-methylimidazolium nitrate, [C1im][NO3], are assigned using ab initio molecular dynamics (AIMD) simulation. AIMD is used at the same level of theory to simulate the known X-ray crystal structure of [C1im][NO3] and a cluster of ionic pairs representing the liquid phase. The calculation of several single particle and collective time correlation functions of velocity forms the basis for the AIMD simulation assignment of the infrared spectra. The AIMD simulation demonstrates that the lift of the degeneracy of the anion asymmetric stretching mode, νas(NO3), due to symmetry breaking and coupling to external modes result in multiple band splitting in the crystal spectrum in the region of the νas(NO3) mode. Owing of the intrinsic anharmonic characteristic of the AIMD simulation, the calculation accounts for the broad band in the high-frequency range of the IR spectrum caused by the cation ν(NH) stretching mode in strong cation–anion hydrogen bond. The AIMD simulation of the liquid captures spectral changes upon melting of [C1im][NO3] due to loosening of the NH···O hydrogen bond and changes in the [NO3]- interaction with other hydrogen atoms of the imidazolium ring. The AIMD simulation assigns the intermolecular stretching mode of the hydrogen bond, ν(NH…O), as the band at 183 cm−1 in the far infrared spectrum of the [C1im][NO3] crystal.

Crystal growth, spectra and laser properties of Tm3+ and Ho3+ co-doped GdScO3 crystal

Tm,Ho:GdScO3 single crystal was grown by the Czochralski method. Its quality and effective segregation coefficient of crystal were characterized, and spectral properties of crystal (100) plane were studied. The absorption cross-section of Tm,Ho:GdScO3 at 793 nm is 1.61 × 10−20 cm2 and emission cross-section at 2020 nm is 1.39 × 10−20 cm2. The laser performance of the crystal by 793 nm LD end-pumped was investigated. The maximum output power of 240 mW was obtained with a slope efficiency of 9.1 % in CW(continuous wave) pump mode. In pulse mode, the maximum average output power of 507 mW was achieved. The maximum slope efficiency of 13.7 % was obtained with 100 Hz and 400 μs. The laser wavelength was 2096 nm. The beam quality factors Mx2/My2 were fitted to be 1.81/1.80. These results indicate that Tm,Ho:GdScO3 crystal is a promising candidate medium for near-infrared laser application.

Microstructural, dielectric, electrical, electromagnetic, and magnetic property enhancements in GdIG /TrIG/ Mn0.2Co0.3Zn0.5Fe2O4 ferrites composites for electronic devices application

Gadolinium garnet ferrite (GdIG) and terbium garnet ferrite (TrIG), known for their favourable magnetic and dielectric characteristics, were combined with doped zinc spinel ferrite (GdIG)x-(TrIG)y/Mn0.2Co0.3Zn0.5Fe2O4(1-x-y) (at x=1 y=0, x=0 y=1, x=y=0.5, x=y=0.25, x=y=0) to achieve improved permittivity, permeability and magnetic properties with reduced magneto-dielectric losses. Our study details the synthesis process and the resulting enhancements in structural, magnetic, and dielectric properties of the prepared samples. Analysis of the X-ray diffraction (XRD) patterns confirmed the presence of a crystalline structure characterized by both cubic spinel and cubic garnet phases in the composites. The microstructures of the composites were analysed with field emission scanning electron microscopy (FESEM), revealing the variation in a grain size from 0.11 μm to 0.96 μm at x =y=0.5. A thorough link between the crystal structure and XRD spectra, transmission electron microscope (TEM), and selected area electron diffraction (SAED) patterns have all been investigated in order to enhance the characterisation of the samples. At 1KHz, the composites exhibit highest electrical resistivity values of 5.9×106 Ωm and 2.6×106 Ωm. With the incorporation of spinel ferrites in garnet ferrite composite (x=y=0.25) the highest value of dielectric constant (885.2) and low value of dielectric loss (0.07) at 100 KHz has been obtained. Permeability values, derived from permittivity data, showed an increase in real permeability values of from 1.4×1012 to 9.2×1017 for x=y=0.5 to x=y=0.25 composite. Vibrating sample magnetometer (VSM) further confirm that the composite x=y=0.25 has highest magnetic saturation (148.8 emu/g), coercivity (502 Oe) and microwave operating frequency (33.6 GHz). The observed high dielectric constant, low loss values, switching field distribution and good magnetic properties suggest the potential suitability of these samples for various electronic devices like: high frequency devices, antennas, switching devices and magnetic recording devices.

Absorption Spectra of AlGaN/GaN Terahertz Plasmonic Crystals-Experimental Validation of Analytical Approach.

Absorption spectra of AlGaN/GaN grating-gate plasmonic crystals with a period from 1 µm to 2.5 µm were studied experimentally at T = 70 K using Fourier-transform infrared spectrometry. The plasmonic crystals exhibit distinct absorption lines of various plasmon harmonics across the 0.5 to 6 THz frequency range, tunable by gate voltage. Cumbersome and time-consuming electromagnetic simulations are usually needed to interpret or predict the grating-gate crystal spectra. In this work, we examine an analytical model and show that it can successfully describe the majority of existing experimental results. In this way, we demonstrate a new analytical platform for designing plasmonic crystals for THz filters, detectors, and amplifiers.

Thin Ga(Sb,P)/GaP quantum wells with indirect band gap: Crystal structure, energy spectrum, exciton recombination and spin dynamics

Heterostructures with thin GaSb layers embedded in a GaP matrix are studied by transmission electron microscopy as well as steady-state and transient photoluminescence. For a single, one monolayer thick deposition with subsequent overgrowth, nonmonotonic Sb segregation results in self-organized Ga(Sb,P) double-quantum well (QW) formation. One QW is positioned deep in GaP at the designated place according to the heterostructure design, and the other QW is in the near surface region after 40 monolayers of GaP overgrowth. Both QWs are characterized by an indirect band gap. The band alignment in the QWs is identified as type I. In spite of the long (up to milliseconds) exciton lifetimes in the QWs in combination with the electron g factor of +2, the emission of the QWs demonstrates a low circular polarization degree in longitudinal magnetic fields as strong as 10 T. We demonstrate that the electron spin polarization in the Ga(Sb,P)/GaP heterostructure subject to a magnetic field occurs in the GaP layer, and spin-polarized charge carriers captured in the QWs store their spin orientation up to the millisecond time range, indicating very long spin relaxation times for the strongly localized electrons in the Ga(Sb,P)/GaP QWs.

Optical transmittance range of High-Temperature stable phase germanium dichalcogenide (GeS2) single crystal grown by the Bridgman method

A high-temperature (HT) stable phase germanium dichalcogenide (GeS2) was grown in an evacuated quartz ampoule to investigate its transparency range. First, as a starting material for the crystal growth of HT-GeS2, GeS2 glass containing HT-GeS2 crystals was synthesized using our previously improved process for synthesizing polycrystalline sulfide compounds in a conventional horizontal furnace. The HT-GeS2 crystal was grown using the Bridgman method under a temperature gradient of 20–30 °C/cm. The grown HT-GeS2 single crystal was easily cleaved along the growth direction, and this cleaved surface was identified as the (001) face using X-ray diffraction (XRD). Single-crystal XRD analysis confirmed the growth of an HT-GeS2 single crystal with a monoclinic structure (space group P21/c) and lattice parameters of a = 6.7061(4) Å, b = 16.0877(13) Å, and c = 11.4242(11) Å, and β = 91.069 (8)°. The optical transmittance spectra of the HT-GeS2 single crystal were measured in the visible and infrared (IR) regions, revealing a transparency range of 0.36–22.5 μm. Differential thermal analysis revealed the melting point of HT-GeS2 as 841 ± 1 °C. The HT-GeS2 single crystal is expected to be a new candidate for IR optical crystal.

Quasi-Dirac points in electron-energy spectra of crystals

Specific properties, such as surface Fermi arcs, features of quantum oscillations and of various responses to a magnetic field, distinguish Dirac semimetals from ordinary materials. These properties are determined by Dirac points at which a contact of two electron-energy bands occurs and in the vicinity of which these bands disperse linearly in the quasimomentum. This work shows that almost the same properties are inherent in a wider class of materials in which the Dirac spectrum can have a noticeable gap comparable with the Fermi energy. In other words, the degeneracy of the bands at the point and their linear dispersion are not necessary for the existence of these properties. The only sufficient condition is the following: In the vicinity of such a quasi-Dirac point, the two close bands are well described by a two-band model that takes into account the strong spin-orbit interaction. To illustrate the results, the spectrum of ZrTe5 is considered. This spectrum contains a special quasi-Dirac point, similar to that in bismuth.

Lattice dynamics of 119Sn impurity in a bcc-Cr crystal

The chromium crystal doped with119Sn isotope was studied using the nuclear resonance inelastic x-ray scattering and first principles calculations. The Sn partial phonon density of states (PDOS) was obtained for three temperatures that correspond to different magnetic states of Cr. At all temperatures, the energy spectrum consists of a broad band around 18 meV and a narrow peak at 43 meV. The additional peak around 39 meV is observed only in the magnetically ordered phases, indicating the influence of magnetic order in chromium on lattice dynamics. The partial PDOS calculated with the antiferromagnetic order on Cr atoms show a very good agreement with the experimental data. It is revealed that the high-energy peak is lying above the phonon spectra of the pure bcc-Cr crystal. These are the local modes with the increased energies due to a strongly reduced distance between Sn and the nearest-neighbor Cr atoms.

Entropy-stabilized materials as a platform to explore terbium-based pyrochlore frustrated magnets

Two decades of work have shown that the physics of Tb-based pyrochlores is controlled by a subtle equilibrium between quadrupole-quadrupole and dipolar-dipolar magnetic interactions, as exemplified by the ordered spin ice Tb2Sn2O7 and the quantum spin liquid candidate Tb2Ti2O7. The high-entropy approach is thus quite promising, as it offers the possibility of a delicate tuning of chemical disorder. In this work, we investigate the entropy-stabilized pyrochlore compound Tb2(TiZrHfGeSn)2O7. We report the lack of long range magnetic order, yet the observed magnetic diffuse scattering is characteristic of antiferromagnetic first-neighbor correlations. The crystal field excitation spectrum, with broaden levels, visibly reflects the smooth environmental disorder of the Tb environment. The low energy dynamics are characterized by a narrow mode at about 0.4 meV, consistent with specific heat. Remarkably, as illustrated by a model of random isotropic shifts of oxygen atoms around Tb ions, the spectral weight of this mode is a direct consequence of deviations from the D3d symmetry at Tb sites. In the light of these results, quadrupolar interactions are also discussed.

Heat Capacity and Features of the Phonon Spectrum of Single Crystals of Solid Solutions of Yttrium-Lutetium Alumogranates

Heat Capacity and Features of the Phonon Spectrum of Single Crystals of Solid Solutions of Yttrium-Lutetium Alumogranates

Indexing neutron transmission spectra of a rotating crystal.

Neutron time-of-flight transmission spectra of mosaic crystals contain Bragg dips, i.e., minima at wavelengths corresponding to diffraction reflections. The positions of the dips are used for investigating crystal lattices. By rotating the sample around a fixed axis and recording a spectrum at each rotation step, the intensity of the transmitted beam is obtained as a function of the rotation angle and wavelength. The questions addressed in this article concern the determination of lattice parameters and orientations of centrosymmetric crystals from such data. It is shown that if the axis of sample rotation is inclined to the beam direction, the reflection positions unambiguously determine reciprocal-lattice vectors, which is not the case when the axis is perpendicular to the beam. Having a set of such vectors, one can compute the crystal orientation or lattice parameters using existing indexing software. The considerations are applicable to arbitrary Laue symmetry. The work contributes to the automation of the analysis of diffraction data obtained in the neutron imaging mode.

The effect of singularities and damping on the spectra of photonic crystals

Understanding the dispersive properties of photonic crystals is a fundamental and well-studied problem. However, the introduction of singular permittivities and damping complicates the otherwise straightforward theory. In this paper, we study photonic crystals with a Drude–Lorentz model for the permittivity, motivated by halide perovskites. We demonstrate how the introduction of singularities and damping affects the spectral band structure and show how to interpret the notion of a “band gap” in this setting. We study a one-dimensional model for which we present explicit solutions.