Bond Lengths Research Articles

Resonance Effects from Substituents on L-Type Ligands Mediate Synthetic Control of Gold Nanocluster Frontier Orbital Energies.

The ligands of metal nanoclusters can be used to control their properties and reactivity, but a framework guiding their use remains elusive. Hammett studies of Au8(PPh3)72+ and Au9(PPh3)83+ nanoclusters with para- and meta-methyl and -methoxy groups indicate that resonance effects, not inductive effects, yield quantitative shifts of the HOMO-LUMO transitions involving orbitals local to the cluster core. Individual ligand exchanges reveal that these shifts are caused by only four of seven ligands, inconsistent with inductive effects. Quantum chemical calculations predict no trend in Au atom charges with respect to Hammett parameter but do predict bond length trends expected for a resonance structure that includes the Au atoms. Computed orbitals show contributions from specific para-OMe oxygen lone pairs to the HOMO, indicating delocalization from the core to specific ligands. These results suggest that resonance structures could be drawn including Au and ligands, guiding efforts to modulate nanocluster electronic structure and energy transfer.

Praseodymium induced symmetry switching and electrochemical characteristics of LaCoO3 nanostructures

A comparative study of the crystal structures and electrochemical characteristics of bulk and nanoscale La1-xPrxCoO3 (x = 0, 0.3 and 0.6) perovskites is made using synchrotron x-ray diffraction, cyclic voltammetry, and galvanostatic charge/discharge methods. It is shown that the sol-gel synthesized nano structures and bulk LaCoO3 exhibit different crystal structures, viz., rhombohedral [a = b = 5.4401 Å, c = 13.134 Å (on hexagonal axes), Z = 6, R3‾c] and monoclinic [am = 5.3865 Å, bm = 5.4482 Å, cm = 7.6365 Å, βm = 89.010°, Z = 4, I2/a], respectively. The evidence for CoO6 octahedra distortion in bulk LaCoO3 is also gathered from the three distinct Raman active modes at 518, 646, and 688 cm−1 emerging due to the Jahn-Teller effect, which, in-turn, reduces the crystal symmetry for achieving structure stabilization. This amounts to changes in Co–O bond lengths and Co–O–Co bond angles with promotion of t2g electron to eg level simultaneously for Co3+(3d6) to attain an intermediate spin state (S = 1) or higher. However, Pr-insertion induces phase transition to orthorhombic in both but with space group Pnma in nanostructures and equivalent Pbnm in bulk. The substitution effect on the specific capacitance (C) is opposite in nature, i.e., while ‘C’ decreases from 149 to 12 F/g in nano structures, it increases from 0.4 to 4 F/g in bulk with increase in Pr-content from x=0 to 0.6. A galvanostatic charge-discharge test of pristine nano LaCoO3 performed at a constant scan rate of 50 mVs−1 reveals electrode electrochemical stability by retaining 96 % of specific capacitance ∼82.5 F/g for 2000 cycles at least. The variation in the crystal structure and bond length and/or angle plays a key role in controlling the electrochemical performance of Pr-substituted LaCoO3 perovskites.

Effect of γ-rays irradiation on the structural, magnetic, and electrochemical properties of ZnMn2O4 nanoparticles

The study explored the effect of gamma-ray irradiation on the physical, magnetic, and electrochemical properties of ZnMn2O4 synthesized by the burning method. On the physical characterization side, the study utilized multiple metrology techniques to determine the impact of radiation dosage on bond lengths, density, crystallite size, micro strain, lattice constant, and dislocation density. No irradiation impact on the sample's tetragonal spinel structure was observed up to 250 kGy doses. However, the lattice parameters increased post-γ-irradiation and were apparent in the morphology change of irradiated samples compared to control spinel. Conversely, the magnetic parameters decreased post-irradiation based on the vibrating-sample magnetometry (VSM) testing of control and γ-irradiated samples. Changes in parameters like saturation magnetization (Ms) and magneton number (nB) can be attributed to ion-induced disorder and cation distribution in irradiated samples. Finally, the electrochemical testing showed supercapacitor behavior for all ZnMn2O4 samples, with a positive impact of radiation on electrical capacitance and stability. While the γ-irradiated sample with a 250 kGy dose showed a capacitance (Csp) of 515 F/g with 87.6% stability, the control sample had a Csp of 123 F/g and 78% stability. ZnMn2O4 material meets the needs of energy storage devices operating at high ionizing radiation doses.

Pressure-driven perfection: Advancing lead-free halide perovskites Rb2AgBiX6 (X = Br, Cl) for optoelectronic applications

This research employs first-principles simulations to systematically study the structural, elastic, electronic mechanical, and optical characteristics of lead free halide Rb2AgBiX6 (X = Br, Cl) perovskites under pressure. The computed structural parameters are in good agreement with previous experimental and theoretical results. The obtained elastic constants met the Born stability requirements, showing that our materials are mechanically stable at variable hydrostatic pressures, as supported by the computed negative formation energy values. The covalent bond exhibits metallic characteristics, and induced hydrostatic pressure leads to a decrease in bond lengths. Mechanical analysis demonstrates that the studied materials are ductile and mechanically stable, with enhanced ductility under pressure. The materials are small band gap (1.30 eV, 1.801 eV for Rb2AgBiX6 (X = Br, Cl, respectively) semiconductors at ambient pressure with superior optoelectronic performance. Under hydrostatic pressure, Rb2AgBiX6 (X = Br, Cl) experiences a reduction in its band gap (0.545 eV, 1.305 eV for Rb2AgBiX6 (X = Br, Cl, respectively), accompanied by improved physical characteristics. This suggests the potential for increased utilization of this material in optoelectronic devices and solar cells compared to ambient pressure conditions.

Exploring the Impact of Elevated Pressure on the Structural Dynamics of TlInS2 Crystal (I): A First-Principles Investigation with XRD, Raman, and Hirshfeld Topology

The structural dynamics of Thallium Indium Disulfide (TlInS2) crystal under elevated pressures were comprehensively investigated using a combination of X-ray diffraction (XRD), Raman spectroscopy via first-principles calculations, and Hirshfeld surface (HS) analysis. This study aims to elucidate pressure-induced modifications in the crystal structure and their associated properties of TlInS2 crystal. The findings reveal significant structural transformations as pressure increases, with XRD patterns indicating lattice compression and a critical transition from semiconductor to conductor at pressure P=6.25GPa [42]. The calculations predict a reduction in bond lengths, specifically S1-In1 and S1-Tl2, alongside a corresponding decrease in lattice parameters and unit cell volume. Raman spectroscopy corroborates these changes through shifts in phonon modes. The HS analysis provides further insights into pressure-dependent alterations in intermolecular interactions, revealing changes in voids and surface characteristics. The data gained from TlInS2's structural behavior under pressure, contributing to the optimization of its functional properties for pressure-tunable applications in high-performance electronic and optoelectronic devices.

Extending the functional form of the methane PES in redundant coordinates for highly excited vibrational energy levels calculation

Potential energy surfaces (PES) of methanewhich are constructed using ten symmetrised combinations of four bond length and six interbond angles are referred to as (10S) PESs At high energy ranges, it was found that (10S) PESs permitted improving by factor of five the fit quality of ab initio electronic energies of methane versus standard nine symmetric coordinates (9S) PES representations both in internal, orthogonal or normal-mode coordinates. We extend predictions of vibrational band origins to spectral range above 10000 cm−1 to help future analyses of experimental spectra. Accuracy at high energies is increased without notable deterioration at low-E levels (rms deviation of 0.26 cm−1). Based on a comparison between various variants of (10S) PESs we expect that new theoretical band origins should have accuracy not worse than 1–3 cm−1 up to 13400 cm−1.

Structure, microstructure, and ESR properties of concentration-dependent Zn1-xMnxO nanoparticles

In this study, the estimated stress, strain, and crystallite sizes of different Mn-doped ZnO nanoparticles were calculated using the Williamson-Hall method and compared with the values obtained from the Debye-Scherrer formula. Moreover, defects, and magnetic properties of Mn-doped ZnO nanoparticles at different concentrations were investigated. The sol-gel method was used to synthesize nanoparticles. The X-ray diffraction and Rietveld analysis results confirm that the desired structure is formed and that no secondary phase is present up to an Mn concentration of x=0.2. In and out of plane lattice parameters, cell volumes, bond length, atomic locality, and dislocation density (δ) were clarified. The grain size of the concentration-dependent samples was provided by scanning electron microscope. Photoluminescence (PL) spectra exhibited ultraviolet emission along with a broad band encompassing violet, blue, and red regions, attributed to defect-related and excitonic emissions. These emissions were notably influenced by synthesis conditions and doping elements and ratios. Electron spin resonance properties of the concentration-dependent samples were analyzed to figure out the g-factor through line widths of pike-to-pike (ΔHPP) of ESR spectra. Mn-doped ZnO nanoparticles exhibited ferromagnetism at room temperature.

Au, Ag, Pb, Pt −doped MoTe2 monolayer as a novel sensor for dissolved gases (CH4, and C2H2): A first-principles study

In this study, C2H2 and CH4 gas molecules adsorption on intrinsic MoTe2 and Au, Ag, Pb, Pt doped MoTe2 by density functional theory (DFT). The adsorption energy, bond length, charge transfer, PDOS and work function are calculated, it can be proved that Ag-MoTe2 have excellent C2H2 and CH4 adsorption performance than Au-MoTe2, Pb-MoTe2 and Pt-MoTe2. However, C2H2 gas molecule can be chemisorbed onto the doped Ag in the modified MoTe2 with a high adsorption energy of 0.923 eV, capturing approximately 0.65 e from the sensing material. Ag-MoTe2 has the better C2H2 and CH4 adsorption performance than Au-MoTe2, Pb-MoTe2 and Pt-MoTe2, as evidenced by the strong overlap of the s, p, d orbitals and the significant reduction of the energy gap from the PDOS. Therefore, suggesting that the Ag-MoTe2 could have potential application in the capture and dissociation of C2H2 and CH4.

Synthesis, Structural, Spectroscopic (NMR, FT-IR and UV-vis), NLO, in silico (ADMET and Molecular Docking) and DFT Investigations of a Flavonol Derivative 2-(4-chlorophenyl)-7-fluoro-3-hydroxy-4H-chromen-4-one

The geometric, spectroscopic and electronic features of the newly synthesized 3-Hydroxy-2-(4-chlorophenyl)-7-fluoro-4H-chromen-4-one have been analyzed using a combination of single crystal XRD, FT-IR, NMR shifts, and UV-Vis. spectroscopic methods both experimentally and theoretically. The molecule has crystallized in orthorhombic space group Pca21 and it has stabilized with C-H···O, O-H···O intra-molecular and O-H···O inter-molecular interactions. The geometric parameters (bond lengths and bond angles), vibrational wavenumbers, 1H and 13C NMR chemical shifts, UV-Vis. electronic transitions, the HOMO (highest occupied molecular orbital) and the LUMO (lowest unoccupied molecular orbital) analyses, NLO (non-linear optical properties) and the MEP (molecular electrostatic potential) surface have been computed by using the DFT/B3LYP quantum chemical method with 6-311++G(d,p) level of theory to compare with the experimental findings. Absorption bands of the molecule have computed around 300 and 360 nm, while observed at 244, 312 and 344 nm in the experimental UV-Vis. spectrum. Moreover, the mean polarizability value of the compound has been calculated 6.47 times greater than urea. The objective of the in silico investigation was to ascertain the biological effect profile of the title compound. The ADMETlab 2.0 web service has been employed to analyze the physicochemical, medicinal chemistry, metabolism, distribution, absorption, excretion and toxicity features of the compound. Its protein kinase CK2 inhibitory activity for the target macromolecule 5M4U has been investigated by means of a molecular docking study to investigate the anti-cancer activity of our flavonol derivative compound.

Bond-slip behavior of Aluminum Alloy (AA) bars for near-surface mounted (NSM) technique

An experimental study consisting of 22 pull-out tests was carried out to investigate the bond-slip performance and load transfer mechanism between near-surface mounted (NSM) Aluminum Alloy (AA) bars and concrete when the AA bars are inserted into pre-cut grooves on the surface of the host structure and bonded with an appropriate bonding agent. The effects of several design parameters were evaluated including bond length, diameter of AA bars, bar surface treatment, and adhesive type. A digital image correlation (DIC) system was used to measure the slips and surface strain and four failure modes were observed in the tests, being concrete splitting failure, epoxy splitting, debonding at the bar-epoxy interface, and AA bar rupture. Results showed that an increase in bond length could make the failure mode more ductile, while AA bars with rough surfaces exhibited a relatively satisfactory bond-slip behavior when a suitable epoxy was used. Finally, the test data from this study were used to examine three bond-slip models based on fiber reinforced polymers (FRP) for the NSM technique. A new bond-slip model considering the influence of the bar external surface was proposed and validated by the test results from both this study and literature.

Quantification of solvent-mediated host-ion interaction in graphite intercalation compounds for extreme-condition Li-ion batteries

Achieving simultaneous fast-charging capabilities and low-temperature adaptability in graphite-based lithium-ion batteries (LIBs) with an acceptable cycle life remains challenging. Herein, an ether-based electrolyte with temperature-adaptive Li+ solvation structure is designed for graphite, and stable Li+/solvent co-intercalation has been achieved at subzero. As revealed by in-situ variable temperature (−20 ℃) X-ray diffraction (XRD), the poor compatibility of graphite in ether-based electrolyte at 25 ℃ is mainly due to the continuous electrolyte decomposition and the in-plane rearrangement below 0.5 V. Former results in a significant irreversible capacity, while latter maintains graphite in a prolonged state of extreme expansion, ultimately leading to its exfoliation and failure. In contrast, low temperature triggers the rearrangement of Li+ solvation structure with stronger Li+/solvent binding energy and shorter Li+–O bond length, which is conducive for reversible Li+/solvent co-intercalation and reducing the time of graphite in an extreme expansion state. In addition, the co-intercalation of solvents minimizes the interaction between Li-ions and host graphite, endowing graphite with fast diffusion kinetics. As expected, the graphite anode delivers about 84% of the capacity at room temperature at −20 ℃. Moreover, within 6 min, about 83%, 73%, and 43% of the capacity could be charged at 25, −20, and −40 ℃, respectively.

Al‐Decorated C20 Fullerene as a Promising Noble Metal‐Free Catalyst for CO Oxidation: A DFT Study

AbstractTo remove the toxic carbon monoxide (CO) gas from the environment, recently, researchers have taken great interest in single‐atom catalysts (SACs). In this study, we investigated various reaction pathways and barrier energies for the CO oxidation process onto Al‐decorated C20 fullerene (Al@C20) employing density functional theory (DFT). The outcomes validate that Al decoration on C20 is energetically stable while the corresponding electronic properties show that the Al atom acts as the reactive site for catalytic activity. The bond distances and larger negative adsorption energies (−0.65 and −2.53 eV) evince that CO and O2 species adsorbed strongly to the Al atom. For the oxidation of CO, two popular mechanisms are examined: Eley Rideal (ER) and Langmuir Hinshelwood (LH). The assessment of energy barriers discloses that the CO oxidation reaction progresses via the LH mechanism. Additionally, the CO + O* → CO2 reaction proceeds very quickly onto the Al@C20 catalyst, with a very small energy barrier (0.13 eV), indicating the excellent catalytic reactivity of the studied catalyst. These results propose that the designed catalyst can be valuable in the progress of novel noble metal‐free catalysts for harmful CO elimination from the environment.

Bundling Effect on Bond and Development Length of Sand-Coated GFRP Bars

Bundling Effect on Bond and Development Length of Sand-Coated GFRP Bars

Correlation of Valence electron structure and properties of monolayer graphene and MX2 (M=Mo, W; X=S, Se, Te): Empirical Electron Theory (EET) investigation

The atomically thin layers of transition-metal dichalcogenide (TMDC) materials have garnered considerable attention due to their exceptional electrical, optical, mechanical, and thermal properties. Hence, it is important to investigate the mechanism of their excellent properties. In this paper, the study is focused on the correlation between valence electron structures (VESs) and mechanical as well as thermal properties of graphene and MX2 (M = Mo, W; X = S, Se, Te) for revealing their essential mechanisms of properties with an empirical electron theory (EET). A model of Young's modulus is built for the monolayer graphene and MX2 (M = Mo, W; X = S, Se, Te) based on the VES, which has been verified by the observed ones of elements in the 4th to 6th periods in the periodic table of elements. The calculated bond lengths and mechanical and thermal properties of graphene and MX2 are in good agreement with experimental ones. The study reveals that the thermal and mechanical properties of MX2 strongly depend on their valence electron structures. It shows that the melting point, cohesive energy, thermal conductivity, and Young's modulus are modulated by covalence electron pair nA, the averaged covalence electron per atom nc/atom, covalence electron pair nA and linear density of covalent electron on the strongest bond ρl, respectively. The study helps explain the thermal and mechanical properties of two-dimensional (2D) materials and also supplies a reference for their design with high performance by modulating their valence electron structures.

Lattice distortion effects in high-entropy oxides: Boosting PMS activation for effective and durable pollutant degradation

Advanced Oxidation Processes (AOPs) are highly effective for pollutant removal, but achieving an optimal combination of high reactivity, corrosion resistance, and long-term stability remains challenging. In this study, we present the synthesis of a distinctive hollow prismatic high-entropy oxide, (Co0.2Ni0.2Mn0.2Cu0.2Zn0.2)3O4, derived from complex coordination polymers. This high-entropy oxide exhibits significant lattice distortion effects compared to conventional (Co1/3Ni1/3Mn1/3)3O4 and Co3O4. These distortions reduce the metal-O bond length, which enhances cyclic stability during peroxymonosulfate (PMS) activation for pollutant degradation. Additionally, the improved interaction between the catalyst and PMS enhances the generation of reactive oxygen species (ROS), leading to superior catalytic degradation activity. Electron paramagnetic resonance (EPR) and other analytical techniques identify ·OH, 1O2, O2−· as the primary active species in the (Co0.2Ni0.2Mn0.2Cu0.2Zn0.2)3O4/PMS system. A degradation mechanism for tetracycline (TC) is also proposed. This study introduces an innovative approach to water treatment by employing high-entropy oxides to activate PMS, demonstrating substantial potential for practical applications.

Hydrothermal synthesis of Gd-doped CaO nanoparticles from lemon peel extract for efficient photocatalytic degradation of methylene blue under UV and sunlight

Water pollution, exacerbated by the improper disposal of non-biodegradable dyes from textile and paper industries, poses a significant global threat. Addressing this challenge, the present study focuses on the photocatalytic degradation of methylene blue (MB), a harmful azo dye, using novel Gd-doped CaO NPs synthesized with waste lemon peel extract (LPE) as a green stabilizing agent. The CaO NPs, calcined at 700 °C and subsequently doped with gadolinium (Gd) at concentrations of 2, 4, and 6 mmol via hydrothermal method, were characterized using various techniques. Fourier Transform Infrared Spectroscopy (FTIR) confirmed presence of Ca-O and Gd-O with the bond lengths of 1.7 Å and 1.2 Å, respectively. UV–Visible spectra revealed a bandgap in the range of 3.28 to 2.50 eV. X-ray Diffraction (XRD) patterns confirmed crystallinity with the crystallite size estimated using the Scherrer and William sons-Hall (W-H) methods ranging from 18 to 38 nm and XRD deduced specific surface area between 47 and 98 m2/g. Dynamic Light Scattering (DLS) showed particle size distribution from 38 to 130 nm, and zeta potential values ranging from −13.5 to −19.9 mV. The photocatalytic activity against MB was tested under UV light and natural sunlight at dye concentrations of 10, 15, and 20 ppm. The 4 mmol Gd-doped CaO NPs achieved a remarkable 98 % degradation efficiency within 2 h of sunlight exposure at a 10 ppm dye concentration. The degradation followed a pseudo-first-order reaction, and a possible degradation pathway was proposed for methylene blue. This study concludes that Gd-doped CaO NPs are highly effective, sustainable, and cost-efficient photocatalysts for wastewater treatment.

Effects of nozzle geometry and fiber orientation on the tensile strength of 3D printed continuous fiber reinforced composites

In material extrusion (MEX) based 3D printing, inter-filament voids are intrinsic to printing process. The void orientation, volume and shape are affected by multiple factors including the nozzle shape, stacking sequence and printing direction. In this study, the adverse effects of the inter-filament voids on tensile properties and damage modes were investigated numerically on 3D printed acrylonitrile butadiene styrene-carbon fiber (ABS/CF) continuous fiber-reinforced composites (CFRCs). Uniaxial tensile simulations were performed considering various nozzle geometries (circular, square), fiber orientations (θ=0o,30o,45o,60o,90o) relative to loading direction, and a regular stacking sequence of extrudates. The extrudate cross-section was modeled either using elliptical or superelliptical extrudates deposited from a circular or square nozzle, respectively. Excellent agreement was seen when the simulated results were benchmarked against several published experimental and numerical work. Simulated results showed that changing the nozzle shape from circular to square improved the mechanical properties across all fiber angles by lowering the void content by 7−8% and increasing the ultimate tensile strength (σT) by 11−18%, tensile stiffness (ET) by 6−8%, and the tensile failure strains (ϵT,fail) by 1−11%. For superelliptical extrudates the number of observed damage modes also reduced, and this is due to a 37.2% and 58.2% improvement in the inter-filament and inter-layer bond lengths, respectively. Also, when fiber angle became increasingly off-axis to tensile load direction, the strengths, moduli, and failure strains reduced for both circular and square nozzles. The significance of using microstructure geometries and explicitly modeling inter-filament voids for simulating MEX printed CFRCs was highlighted by comparing these results with both analytical calculations and simulated results of homogeneous solid CFRC blocks without voids.

Advanced Electron Microscopy Characterisation of Aluminium-Oxygen Coordination in Catalyst Supports

Performance of alumina-supported catalyst systems are significantly affected by how the tetrahedral (Al-O4) and octahedral (Al-O6) coordination are mixed and blended with each other. Characterisation of aluminium-oxygen coordination is thus important to understand how catalysts interact with alumina at the microscopic level. Here we report the application of two advanced electron microscopy techniques on aluminium-oxygen coordination. The first technique is electron energy loss spectroscopy (EELS) that can reveal detailed electronic structure profile of aluminium valence band to analyse how aluminium is coordinated by oxygen. The second technique is pair distribution function (PDF) based on electron diffraction (ED), employed to measure aluminium-oxygen bond lengths associated with the coordination geometry.

Modulating the Electronic Structure of Cobalt-Vanadium Bimetal Catalysts for High-Stable Anion Exchange Membrane Water Electrolyzer.

Modulating the electronic structure of catalysts to effectively couple the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is essential for developing high-efficiency anion exchange membrane water electrolyzer (AEMWE). Herein, a coral-like nanoarray composed of nanosheets through the synergistic layering effect of cobalt and the 1D guiding of vanadium is synthesized, which promotes extensive contact between the active sites and electrolyte. The HER and OER activities can be enhanced by modulating the electronic structure through nitridation and phosphorization, respectively, enhancing the strength of metal-H bond to optimize hydrogen adsorption and facilitating the proton transfer to improve the transformation of oxygen-containing intermediates. Resultantly, the AEMWE achieves a current density of 500 mA cm-2 at 1.76 V for 1000 h in 1.0 M KOH at 70°C. The energy consumption is 4.21 kWh Nm-3 with the producing hydrogen cost of $0.93 per kg H2. Operando synchrotron radiation and Bode phase angle analyses reveal that during the high-energy consumed OER, the dissolution of vanadium species transforms distorted Co-O octahedral into regular octahedral structures, accompanied by a shortening of the Co-Co bond length. This structural evolution facilitates the formation of oxygen intermediates, thus accelerating the reaction kinetics.

Temperature dependence of Ce luminescence characteristics in LaBr3: Ce crystal

Despite the large interest in the scintillation properties of LaBr3:Ce, a detailed understanding of the underlying mechanism of temperature-dependence properties of Ce luminescence remains elusive. This study introduces a self-designed spectral apparatus to explore these properties in LaBr3:5%Ce. We observed a redshift phenomenon and band changes in the emission peak bands, indicating a reduction of the bond length between Ce and the host with increasing temperature. Moreover, the probability of low-energy peak emission decreases and the probability of high-energy peak emission increases, with increasing temperature was observed, suggesting a correlation with the proximity of Ce's 4f energy level to the valence band. Utilizing intensity parameters from the spectra, we identified the impact of temperature on LaBr3:Ce's self-absorption effect, revealing a significant self-absorption effect at the high-energy peak for the first time. A simple self-absorption model indicated that, despite high quantum efficiency of Ce, the overall self-absorption is minimal, establishing a correlation between the self-absorption coefficient of the high-energy peak and overall absorption. This research offers insights for developing radiation-resistant high-temperature luminescent devices and advances the field of high-temperature luminescent materials.