Crystallographic Axes Research Articles

LiLnGeS4 (Ln=La-Nd): Designing High Performance Infrared Nonlinear Optical Sulfides through "Band Reformation of AGS".

AgGaS2 (AGS) is the most commonly used commercial infrared nonlinear optical (IR NLO) material. However, AGS has a narrow band gap (Eg=2.58 eV) and a low laser-induced damage threshold (LIDT), primarily attributed to its mobile liquid-like Ag+ constituent and the unstable Ag-S chemical bond. Herein, we propose a "band reformation of AGS" strategy, which leads to the successful syntheses of four lanthanide sulfides, LiLnGeS4 (Ln=La-Nd), crystalizing in an asymmetric Ama2 structure. LiLaGeS4 demonstrates that eliminating the presence of Ag-4d band increases the Eg to 3.32 eV and enhances the LIDT (14-29×AGS, measured by both powder and single crystal); while increasing the nonbonding density of states of the S-3p band enhances the 2nd-nonlinear optical coefficient (1.06×AGS). Besides, the bond length discrepancy between [LiS4], [GeS4] and [LaS8] units leads to a moderate birefringence (Δn=0.052). Such a unique structure further results in extremely small thermal expansion with αL=0.41-1.74×10-5 K-1, along different crystallographic axes. Our theoretical studies indicate that the synergy of the structure building units contribute to the second harmonic generation performance. These results suggest that the "band reformation of AGS" strategy provides effective guidance to discover new NLO crystals with optimized performance.

LiLnGeS4 (Ln=La−Nd): Designing High Performance Infrared Nonlinear Optical Sulfides through “Band Reformation of AGS”

AbstractAgGaS2 (AGS) is the most commonly used commercial infrared nonlinear optical (IR NLO) material. However, AGS has a narrow band gap (Eg=2.58 eV) and a low laser‐induced damage threshold (LIDT), primarily attributed to its mobile liquid‐like Ag+ constituent and the unstable Ag−S chemical bond. Herein, we propose a “band reformation of AGS” strategy, which leads to the successful syntheses of four lanthanide sulfides, LiLnGeS4 (Ln=La−Nd), crystalizing in an asymmetric Ama2 structure. LiLaGeS4 demonstrates that eliminating the presence of Ag‐4d band increases the Eg to 3.32 eV and enhances the LIDT (14–29×AGS, measured by both powder and single crystal); while increasing the nonbonding density of states of the S‐3p band enhances the 2nd‐nonlinear optical coefficient (1.06×AGS). Besides, the bond length discrepancy between [LiS4], [GeS4] and [LaS8] units leads to a moderate birefringence (Δn=0.052). Such a unique structure further results in extremely small thermal expansion with αL=0.41–1.74×10−5 K−1, along different crystallographic axes. Our theoretical studies indicate that the synergy of the structure building units contribute to the second harmonic generation performance. These results suggest that the “band reformation of AGS” strategy provides effective guidance to discover new NLO crystals with optimized performance.

How Do Gepotidacin and Zoliflodacin Stabilize DNA Cleavage Complexes with Bacterial Type IIA Topoisomerases? 1. Experimental Definition of Metal Binding Sites

One of the challenges for experimental structural biology in the 21st century is to see chemical reactions happen. Staphylococcus aureus (S. aureus) DNA gyrase is a type IIA topoisomerase that can create temporary double-stranded DNA breaks to regulate DNA topology. Drugs, such as gepotidacin, zoliflodacin and the quinolone moxifloxacin, can stabilize these normally transient DNA strand breaks and kill bacteria. Crystal structures of uncleaved DNA with a gepotidacin precursor (2.1 Å GSK2999423) or with doubly cleaved DNA and zoliflodacin (or with its progenitor QPT-1) have been solved in the same P61 space-group (a = b ≈ 93 Å, c ≈ 412 Å). This suggests that it may be possible to observe the two DNA cleavage steps (and two DNA-religation steps) in this P61 space-group. Here, a 2.58 Å anomalous manganese dataset in this crystal form is solved, and four previous crystal structures (1.98 Å, 2.1 Å, 2.5 Å and 2.65 Å) in this crystal form are re-refined to clarify crystal contacts. The structures clearly suggest a single moving metal mechanism—presented in an accompanying (second) paper. A previously published 2.98 Å structure of a yeast topoisomerase II, which has static disorder around a crystallographic twofold axis, was published as containing two metals at one active site. Re-refined coordinates of this 2.98 Å yeast structure are consistent with other type IIA topoisomerase structures in only having one metal ion at each of the two different active sites.

Tri-axial magnetic alignment and magnetic anisotropies in misfit-layered calcium-based cobaltites doped with rare-earth ions

In this study, we introduce an original method for quantifying tri-axial magnetic anisotropy in [Ca2CoO3-δ]0.62CoO2, and its rare earth (RE)-doped variants, [(Ca1-xREx)2CoO3-δ]0.62CoO2, utilizing a modulated rotating magnetic field of 10 T. Our findings reveal a significant correlation between the magnetic anisotropy and local structure of RE ions, particularly bond lengths and coordination numbers, which influence the magnetization axes of these magnetically aligned powders. We introduce an analytical methodology employing linear equations to calculate the magnetic susceptibilities along distinct crystallographic axes, enabling the prediction of tri-axial magnetic anisotropies at elevated concentrations of Er ions. This research not only advances our understanding of magnetic anisotropy control but also paves the way for the successful fabrication of triaxially-aligned ceramics using magneto-science techniques.

Simultaneous vector magnetometry based on fluorescence polarization of NV centers ensemble in diamond

The nitrogen-vacancy (NV) centers ensemble has extensive application prospects in vector-magnetic-field measurement due to its accurate and fixed spatial orientations along the crystallographic axes of diamonds. However, to address signals of NV centers along all four axes, a large bias magnetic field sufficient to spectrally separate their resonances is typically inevitable, which may affect the magnetic substance under test and require multiple-frequency microwaves to interrogate signals of the four axes. Here, we demonstrate an NV-based simultaneous vector magnetometer that works at a bias field as low as just separating the resonant peaks of |ms=±1 states and utilizes a single-frequency microwave. By simultaneously detecting the fluorescence at specific optical polarization angles in three orthogonal directions and determining the transformation matrix in advance, all the Cartesian components of the magnetic field under test are distinguished. The experimentally achieved magnetic-field sensitivity is 63 nT/Hz, and the bias field is reduced to around 11 Gauss (still reducible by narrowing the linewidth) in ambient conditions. The proposed methods dramatically reduce the bias field for NV-based simultaneous vector magnetometers and potentially expand their applications in biological science, materials science, and industrial noninvasive detection.

Quantum size effects in ultra-thin YBa2Cu3O7 − x films

The d-wave symmetry of the order parameter with zero energy gap in nodal directions stands in the way of using high-temperature superconductors for quantum applications. We investigate the symmetry of the order parameter in ultra-thin YBa2Cu3O7 − x (YBCO) films by measuring the electrical transport properties of nanowires aligned at different angles relative to the main crystallographic axes. The anisotropy of the nanowire critical current in the nodal and antinodal directions reduces with the decrease in the film thickness. The Andreev reflection spectroscopy of the nanoconstrictions shows the presence of a thickness-dependent energy gap that does not exist in bulk YBCO. We find that the thickness-dependent energy gap appears due to the quantum size effects in ultra-thin YBCO films that open the energy gap along the entire Fermi surface. The fully gapped state of the ultra-thin YBCO films makes them a promising platform for quantum applications, including quantum computing and quantum communications.

ELECTROMECHANICAL PROGRAMMER FOR ACOUSTOELECTRONIC SENSORS OF PHYSICAL QUANTITIES

An electromechanical programmer is described, intended for programming an acoustoelectronic angular displacement meter, constructed on the basis of the effect of dependence of the phase velocity of surface acoustic waves on the direction of propagation relative to the crystallographic axis of a piezoelectric sound conductor.

Crystal Growth of LiNa5Mo9O30 Crystals of High Optical Quality

The bulk of the LiNa5Mo9O30 (LNM) crystals were successfully grown in the [010] and [001] directions without internal inclusions and cracks, using the Czochralski method with a low temperature gradient. The crystal grown in the [010] direction showed a tendency to twinning. The crystal grown in the [001] direction demonstrated high structural perfection (FWHM = 13″) for the (001) plane and high optical quality Δn ≈ 2 × 10−5. The laser-induced damage threshold was measured along a, b and c axes and was 12.2, 27.0 and 27.5 J/cm2, respectively. The thermo-optical coefficient dn/dT was measured for the main crystallographic axes, which was −5.75 × 10−6, −20.2 × 10−6 and 3.65 × 10−6 K−1 along the a, b and c axes, respectively. The second harmonic generation (SHG) was conducted in the crystalline LNM sample. The maximum efficiency value of 3.5% at a pump power of 12 W was achieved.

Anisotropy-driven magnetic phase transitions in SU(4)-symmetric Fermi gas in three-dimensional optical lattices

Abstract We study SU(4)-symmetric ultracold fermionic mixture in the cubic optical lattice with the variable tunneling amplitude along one particular crystallographic axis in the crossover region from the two- to three-dimensional spatial geometry. To theoretically analyze emerging magnetic phases and physical observables, we describe the system in the framework of the Fermi-Hubbard model and apply dynamical mean-field theory. We show that in two limiting cases of anisotropy there are two phases with different antiferromagnetic orderings in the zero temperature limit and determine a region of their coexistence. We also study the stability regions of different magnetically-ordered states and density profiles of the gas in the harmonic optical trap.

Crystal structure of propane-1,3-diaminium squarate dihydrate.

Propane-1,3-diaminium squarate dihydrate, C3H12N2 2+·C4O4 2-·2H2O, results from the proton-transfer reaction of propane-1,3-di-amine with squaric acid and subsequent crystallization from aqueous medium. The title compound crystallizes in the tetra-gonal crystal system (space group P4bm) with Z = 2. The squarate dianion belongs to the point group D 4h and contains a crystallographic fourfold axis. The propane-1,3-diaminium dication exhibits a C 2v -symmetric all-anti conformation and resides on a special position with mm2 site symmetry. The orientation of the propane-1,3-diaminium ions makes the crystal structure polar in the c-axis direction. The solid-state supra-molecular structure features a triperiodic network of strong hydrogen bonds of the N-H⋯O and O-H⋯O types.

Magnetic anisotropy of L1[formula omitted] FeNi (001), (010), and (111) ultrathin films: A first-principles study

In previous experiments, L10 FeNi thin films with different surfaces, including (001), (110), and (111), were produced and studied. Each surface defines a different alignment of the crystallographic tetragonal axis with respect to the film’s plane, resulting in different magnetic anisotropies. In this study, we use density functional theory calculations to examine three series of L10 FeNi films with surfaces (001), (010), and (111), and with thicknesses ranging from 0.5 to 3 nm (from 4 to 16 atomic monolayers). Our results show that films (001) have perpendicular magnetic anisotropy, while (010) favor in-plane magnetization, with a clear preference for the tetragonal axis [001]. We proposed calling this type of in-plane anisotropy fixed in-plane. A film with a surface (111) and a thickness of four atomic monolayers has a magnetization easy axis almost perpendicular to the plane of the film. As the thickness of the (111) film increases, the direction of magnetization rotates towards a tetragonal axis [001], positioned at an angle of about 45° to the plane of the film. Furthermore, the most significant changes in spin and orbital magnetic moments occur at a depth of about three near-surface atomic monolayers. Ultrathin L10 FeNi films with varying magnetic anisotropies may find applications in spintronic devices.

Investigations of magnetic and thermal expansion properties of two cobalt(II) metal-organic frameworks constructed by mixed bipyridyl-tetracarboxylate strategy

We report the syntheses, crystal structures, adsorption behavior, thermal expansion behavior, and magnetic properties of two cobalt(II) metal-organic frameworks (MOFs), {[Co(btca)1/2(bpe)(H2O)2]·bpe}n (1) and {Co(btca)1/2(bpe)(DMF)}n (2, H4btca = 1,2,4,5-benzenetetracarboxylic acid; bpe = 1,2-di(4-pyridyl)ethane), constructed using mixed bipyridyl and tetracarboxylate ligands. Single-crystal X-ray diffraction (SC-XRD) indicates that the change of synthetic solvents leads to a significant tuning of structural dimensionality from 2D to 3D framework. Temperature-dependent SC-XRD reveals anisotropically negative and positive thermal expansion of the compounds identified along different crystallographic axes within the frameworks over a 120–400 K temperature range. N2 adsorption measurements indicate a nonporous and ultramicroporous framework for 1 and 2, respectively. Magnetic measurements indicate an easy-plane magnetic anisotropy of the Co2+ ions in the MOFs, with experimental D values of 63.1 and 87.1 cm−1. The ac susceptibility measurements of 1 and 2 show field-induced slow magnetic relaxation below 6 K through different relaxation dynamics. This work not only provides two new cobalt(II) SIM-MOFs, but also presents an effective bipyridyl-tetracarboxylate strategy for designing and building framework materials with interesting magnetic and mechanical properties.

Two orientation effects and large anisotropy of parameters in piezo-active 2–1–2 composites based on [0 1 1]-poled crystals

The results of a comparative study on piezo-active 2–1–2 composites with two ferroelectric components are discussed. The composite structure combines elements of 2–2 (laminar) and 1–3 (fibrous) connectivity patterns. The first component in each composite is domain-engineered [0 1 1]-poled single crystal with macroscopic mm2 symmetry and high piezoelectric activity. The second component is a poled ferroelectric ceramic that is represented by parallel rods in the shape of an elliptic cylinder with a large ratio of semi-axes at its base. The first orientation effect is appreciable due to rotations of the main crystallographic axes X and Y around Z || OX 3 by an angle α in each crystal layer. Rotation of the ceramic rod bases by an angle γ in a polymer medium leads to the second orientation effect in the 2–1–2 composite. The two orientation effects contribute to a large anisotropy of electromechanical coupling factors k3j∗ , energy-harvesting figures of merit (FOM) (Q3j∗)2 and modified FOM F3j∗σ for a stress-driven harvester. The large level of (Q32∗)2 , (Q33∗)2 , F32∗σ and F33∗σ (these parameters are of the order of 10−11–10−10 Pa−1) indicates that the studied composites are suitable for piezoelectric sensors, transducers and energy-harvesting systems. New m—α diagrams put forward in the present study show regions wherein the large anisotropy of the effective parameters ( |k33∗ / k3f∗|⩾5 , (Q33∗/Q3f∗ )2 ⩾10 and F33∗σ/F3f∗σ⩾10 , f = 1 and 2) is achieved when changing the volume fraction m of the single crystal and the rotation angle α. As a result, the leading role of the first orientation effect is emphasised.

Gemological Characteristics of Blue-Violet Cordierite

Cordierite is a violet-blue gem mineral primarily composed of magnesium aluminum silicate. This study employed three samples of Mg-cordierite and conducted tests on their gemological characteristics, spectroscopic features, and chemical composition using Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, ultraviolet spectrophotometry, X-ray photoelectron spectroscopy (XPS), and electron microprobe. The study also explored and analyzed the polychroism and coloration mechanisms of the samples. The results indicate that the lattice vibrations of the Mg-cordierite samples differ along the directions parallel to the a, b, and c crystallographic axes, leading to certain variations in spectral characteristics among these directions. The article provides experimental evidence for the reasons for the polychroism of cordierite in different crystal axes, which is of great significance in the quality evaluation of cordierite.

Controlling the columnar-to-equiaxed transition and crack propagation behavior of laser welded Al–Li alloy reinforced with TiC nanoparticles

The predominant method for improving the mechanical characteristics of aluminum-lithium (Al–Li) alloys during laser welding is by regulating the transition from columnar crystals to equiaxed crystals. The transition is facilitated through the incorporation of TiC particles, which play a crucial role in augmenting the strength and toughness of the aluminum alloy. The inclusion of TiC particles offers a new opportunity to enhance the utilization of Al–Li alloys in laser welding procedures. The main aim of this study is to control the transition from columnar to equiaxed crystal structures by creating a TiC nanoparticle-reinforced aluminum alloy filler wire. This is intended to improve the properties of laser-welded joints. The study investigates the impact of different TiC particle contents on the microstructural characteristics. The presence of TiC particles is noted to enhance the transformation of columnar crystals into equiaxed crystals in the welded joints, resulting in a refined microstructure. The augmentation of particle content results in a notable reduction in the average grain size, decreasing from 78.25 μm to 37.15 μm. This alteration shifts the directional growth preference from specific crystallographic axes to a stochastic trajectory. Significantly, when the particle content reaches 0.6 wt%, remarkable enhancements in both tensile strength and elongation are evident, resulting in an ultimate tensile strength of 318 MPa and an elongation of 4.8 %. The dispersed configuration of TiC particles plays a pivotal role in hindering the movement of dislocations, consequently increasing the energy necessary for this mechanism. Moreover, the existence of these particles at grain boundaries impedes the propagation of cracks by altering the direction of the crack path, absorbing additional energy, and consequently improving toughness. An evident pattern emerges when examining higher particle concentrations, indicating that a decrease in ultimate tensile strength is concomitant with an increase in elongation.

Application, structure, salts and complexes of lidocaine: a review. Part V. structure of bis(lidocaine) tetrachloridocuprate(II)

The review focuses on lidocaine (2-(diethylamino)-N-(2,6-dimethylphenyl)acetamide): in the first part, its use in various branches of medicine, as well as the structure of lidocaine, its salts and molecular complexes was discussed; in the second part the use of lidocaine in the composition of deep-eutectic solvents (DES), DES-microemulsions and complexes of lidocaine with zinc, copper, cobalt, platinum and iron was considered; in the 3rd the structure of bis(lidocaine) tetrachlorido-zincate(II) was considered, in the 4th part the structure of bis(lidocaine) tetrachloridoferrate(III) chloride was discussed, this part reports on the synthesis and structure of bis(lidocaine) tetra-chloridocuprate(II), (LidH)2[CuCl4], which crystallizes in the monoclinic space group P21/c with a = 15.7831(2), b = 24.2992(2), c = 17.8748(2) Å, β = 104.874(1)°, V = 6625.58(13) Å3, Z = 8, and Dc = 1.355 Mg/m3. The coordination of the Cu2+ ions with chlorine atoms generates two differently distorted tetrahedral anions [CuCl4]2–, while four protonated cations LidH+ remain in an outer coordination sphere. Anions and cations are associated by hydrogen bonds of the N–H···Cl type to form the 2{(LidH)2[CuCl4]} dimer, in which the distance between two copper atoms is 8.95 Å (c/2). With the help of hydrogen bonds of the type N–H···O and N–H·Cl, each dimer is connected with four neighboring dimers, resulting in a three-dimensional structure in which dimers lie at an angle of 28.39° to the a crystallographic axis in the ab planes located at a distance of 10.67 Å from each other.

Effect of Solvent Composition on Non-DLVO Forces and Oriented Attachment of Zinc Oxide Nanoparticles.

Oriented attachment (OA) occurs when nanoparticles in solution align their crystallographic axes prior to colliding and subsequently fuse into single crystals. Traditional colloidal theories such as DLVO provide a framework for evaluating OA but fail to capture key particle interactions due to the atomistic details of both the crystal structure and the interfacial solution structure. Using zinc oxide as a model system, we investigated the effect of the solvent on short-ranged and long-ranged particle interactions and the resulting OA mechanism. In situ TEM imaging showed that ZnO nanocrystals in toluene undergo long-range attraction comparable to 1kT at separations of 10 nm and 3kT near particle contact. These observations were rationalized by considering non-DLVO interactions, namely, dipole-dipole forces and torques between the polar ZnO nanocrystals. Langevin dynamics simulations showed stronger interactions in toluene compared to methanol solvents, consistent with the experimental results. Concurrently, we performed atomic force microscopy measurements using ZnO-coated probes for the short-ranged interaction. Our data are relevant to another type of non-DLVO interaction, namely, the repulsive solvation force. Specifically, the solvation force was stronger in water compared to ethanol and methanol, due to the stronger hydrogen bonding and denser packing of water molecules at the interface. Our results highlight the importance of non-DLVO forces in a general framework for understanding and predicting particle aggregation and attachment.

Evidence of multifunctional properties of ferromanganite La0.5Ca0.5Mn0.5Fe0.5O3

Synthesis and characterization of the magnetic and electrical properties of the perovskite-type ferro-magnetite La0.5Ca0.5Mn0.5Fe0.5O3 are reported. Structural analysis reveals crystallization of the material in an orthorhombic structure, space group Pbnm (#62). The optical response suggests semiconductor-type behavior with bandgap Eg=2.3 eV. Susceptibility curves as a function of temperature and magnetization as a function of applied field suggest a soft ferromagnetic type response below room temperature, with evidence of disorder characterized by magnetic irreversibility at low temperatures and low applied fields. Resistivity measurements as a function of temperature and corroborate the semiconductor nature of the material and hysteretic I-V curves enhance its applicability in programmable logic memory devices. Band structure calculations around the Fermi level result in two different band gap values for the two spin up and spin down polarizations, as expected in ferromagnetic semiconductor materials. The hybridizations observed in the density of states curves as a function of energy suggest that the ferromagnetic character is due to double exchange mechanisms, coexisting with antiferromagnetic super-exchange, which is essentially due to the disorder of Fe3+ and Mn4+ cations in the octahedra along the three crystallographic axes.

Determination of the internal structural heterogeneity of natural diamond: Methodological aspects of using confocal Raman spectroscopy with polarization analysis

Aim. To describe a technique for studying the internal structural heterogeneity of natural diamond crystals, based on confocal Raman spectroscopy with polarization analysis, including angular resolution, at high spectral (0.5–0.6 cm–1) and spatial (1 μm) resolution. Results. The parameters of the F2g vibrational mode in diamond (position, width, intensity, shape, including the Gaussian and Lorentzian contributions to the broadening) are determined by the superposition influence of a number of factors, including the type and content of structural stresses, deformations, various types of defects, as well as orientation of crystallographic axes of the crystal relative to the directions of incident and scattered rays and the directions of their electric polarization vectors. The proposed analytical technique includes: (1) analysis of the crystallographic orientation of the sample in the spectrometer coordinate system and possible misorientations of its fragments with an error of ≈8–15°; (2) visualization of the distribution of structural stresses, deformations, twins, impurity defects and their associates based on sample surface mapping by spectral parameters of the F2g vibration mode; (3) obtaining statistical characteristics of the internal structural heterogeneity of the samples based on diagrams of spectral parameter frequency with a statistically significant number (≈103): unimodality (uni-, bimodal distributions) and distribution dispersion (from ≈0.1 to ≈0.6 cm–1 for width and from ≈0.04 to ≈0.6 cm–1 for line position). The procedure was tested using two synthetic CVD diamond single crystals doped with nitrogen and boron. The possibility of typification of natural samples by statistical characteristics of internal heterogeneity is considered using the example of samples from kimberlite pipes of Yakutia and placers of the Western Cis-Urals. Conclusions. A method for determining the internal structural heterogeneity of natural diamond crystals based on confocal Raman spectroscopy with polarization analysis is proposed. The possibility of using statistical characteristics of heterogeneity as a typomorphic feature of the original diamond source is demonstrated. The proposed diagrams are promising for sample comparison and typification.

Anisotropic quasi-static permittivity of rare-earth scandate single crystals measured by terahertz spectroscopy

We report the real-valued static and complex-valued quasi-static anisotropic permittivity parameters of rare-earth scandate orthorhombic single crystal GdScO3 (GSO), TbScO3 (TSO), and DyScO3 (DSO). Employing continuous-wave terahertz spectroscopy (0.2–1 THz), the complex permittivity was extracted using an anisotropic ambient-film-ambient model. Data obtained from multiple samples of the same oxides and different surface cuts were analyzed simultaneously. The zero-frequency limit of the modeled data indicates that at room temperature the real part of the dielectric tensor components for GSO are ɛa = 22.7, ɛb = 19.3, and ɛc = 28.1; for DSO, ɛa = 20.3, ɛb = 17.4, and ɛc = 31.1; and for TSO, ɛa = 21.6, ɛb = 18.1, and ɛc = 30.3, with a, b, and c crystallographic axes constituting the principal directions for the permittivity tensor. These results are in excellent agreement with expectations from theoretical computations and with scarcely available data from previous experimental studies. Furthermore, our results evidence a noticeable attenuation, which increases with frequency, and are very significant especially at the higher frequency end of the measurement and along the c-direction in all samples. We suggest the attenuation is most likely caused by the onset of absorption due to long-wavelength active optical phonon modes. These results are important for electronic and potential sub-terahertz applications (e.g., quarter-wave plate) benefiting from the large index contrast along different directions in these materials.