Vibrational Frequencies Research Articles

Large Local Internal Stress in an Elastically Bent Molecular Crystal Revealed by Raman Shifts.

The structural dynamics involved in the mechanical flexibility of molecular crystals and the internal stress in such flexible materials remain obscure. Here, the study reports an elastically bending lipidated molecular crystal that shows systematic shifts in characteristic vibrational frequencies across the bent crystal region - revealing the nature of structural changes during bending and the local internal stress distribution. The blueshifts in the bond stretching modes (such as C═O and C-H modes) in the inner arc region and redshifts in the outer arc region of the bent crystals observed via micro-Raman mapping are counterintuitive to the bending models based on intermolecular hydrogen bonds. Correlating these shifts with the trends observed from high-pressure Raman studies on the crystal reveals the local stress difference between the inner arc and outer arc regions of the bent crystal to be ≈2GPa, more than an order of magnitude higher than the previously proposed value in elastically bending crystals. High local internal stress can have direct ramifications on the properties of molecular piezoelectric energy harvesters, actuators, semiconductors, and flexible optoelectronic materials.

Topological structures and adsorption properties of the [Fe4S4] clusters

The [Fe4S4] compositions are ubiquitous in biological systems as integral parts of the complex catalytic mechanisms as in hydrogenases and nitrogenases. The current reports about [Fe4S4] species are based on the cube-like structure framework. Here, the topological structures, stability and electronic properties of gas phase [Fe4S4]+, [Fe4S4]0 and [Fe4S4]− are analyzed. It is found that ground state structures of these three clusters have similar cubic cages but different symmetries and spin multiplicities. The molecular dynamics simulations demonstrate that the cubic cage remains thermodynamically stable at 700 K. The density of states show that the charge state is the key to affect electronic behaviors of them even under the same structural framework. The molecular orbitals show that the LUMO orbitals are distributed throughout whole structures, showing great delocalized characteristics, especially for the anionic [Fe4S4]−, while the HOMO orbits are mainly localized in Fe-S bonds, which are also confirmed by the electron localization function analyses. After one CO molecule is adsorbed on these clusters, it prefers to locate at the Fe atoms. Moreover, the C–O bond length and vibration frequency of the [Fe4S4]−-CO undergone a significant red shift. Our work shows that the [Fe4S4]− may act as a potential catalyst for activating the C–O bond.

ClSO and ClSO2 photochemistry: Implications for the Venusian atmosphere.

The electronic structure and spectroscopy of ClSOx (x = 1 and 2) isomers were investigated using coupled cluster theory and multireference interaction methods. In this study, the equilibrium geometry and harmonic vibrational frequencies of these isomers in their ground electronic state were shown. Our analysis of the vertical excitation energy and potential energy surface showed the photochemical instability of ClSO for wavelengths below 280nm. Furthermore, the photodissociation of ClSO was unlikely to cause the formation of diatomic ClS. At the same time, ClSO could form atomic chlorine and SO as a result of photodissociation through the repulsive states. In the case of ClSO2, a novel weakly bound Cl-SO2 isomer was identified, indicating the potential influences on the chlorine and SO2 reactions. The potential energy surface of the most stable ClSO2 isomer also indicated the potential production of SO2 in both its ground and excited states. In addition, the electronic spectrum of ClSO2 was predicted to be broad, with numerous significant peaks in the near-UV‒Vis range. Valuable new insights into the chemical role of chlorine and sulfur in Venus's atmosphere were provided, along with a discussion of a potential mechanism contributing to the H2O and SO2 depletion in Venus's atmosphere.

Cyanonaphthalene and cyanonaphthyl radicals: Vibrational structures via computed negative ion photoelectron spectra and thermochemistry of 1- and 2-cyanonaphthalene.

A double harmonic oscillator model is applied to compute the negative ion photoelectron spectra (NIPES) of the 1- and 2-cyanonaphthalene (CNN) radical anions. The computed Franck-Condon factors utilize optimized structures and harmonic vibrational frequencies obtained using density functional theory with the B3LYP 6-311++G (2d,2p) basis set while considering the mode-mixing Duschinsky effects. To test the accuracy of our model, the NIPES of α and β naphthyl radical anions were computed, and a strong agreement between the slow electron velocity-map ion imaging spectra and the predicted spectra was found. The adiabatic electron affinities (EAs) of the ground singlet states (S0) in 1-CNN and 2-CNN are 0.856 and 0.798eV, respectively. The origin of the lowest-lying triplet (T1) states in 1-CNN and 2-CNN is found to be 3.226 and 3.266eV, resulting in singlet-triplet energy splittings (ΔEST) of 2.370 and 2.468eV, respectively. Both the NIPES for electron detachment to the S0 and T1 states exhibit well-resolved vibrational features, allowing for the assignment of several vibrational fundamental frequencies. Following deprotonation, several isomers are formed, with the most stable deprotonated radical anions in 1-CNN and 2-CNN, corresponding to the removal of the most acidic proton, with EAs of 2.062 and 2.16eV. The rich spectroscopic and thermochemical data obtained in the current study make the CNN radical anions and their deprotonated species interesting systems for investigation in gas-phase, negative-ion experiments.

The impact of mechanical vibration at cathode on hydrogen yields in water electrolysis

This study investigates the utilization of mechanical vibration to enhance the hydrogen evolution reaction (HER) in electrolysis processes. By varying the force magnitude and frequency of mechanical vibration, significant improvements in HER efficiency were observed. Specifically, the mechanical vibration-assisted electrolysis with a hitting frequency of 3 hits per second and 157.2698 Kg. m−2 hitting force improved the HER current density by 128 % compared to untreated water electrolysis. Linear sweep voltammetry (LSV) data for the graphite electrode revealed a distinct reduction peak at 1 V, indicating a favorable electrochemical reduction reaction influenced by mechanical vibration. The frequency of mechanical vibration significantly impacted the LSV response, with variations in current values across different conditions. Mechanistically, mechanical vibration disrupted intermolecular forces, facilitating better electrode-bubble interactions and accelerating reaction kinetics. Additionally, changes in pH levels induced by mechanical vibration further enhanced HER efficiency. These results suggest that integrating mechanical vibration into electrolysis systems significantly improves HER performance, contributing to the advancement of more efficient and sustainable hydrogen production technologies, which are crucial for achieving net-zero emission targets.

Strain characteristics of reinforced soft clay around tunnel under metro loads

This study investigates the Strain characteristics of reinforced soft clay surrounding a tunnel subjected to cyclic loading, employing the Global Digital Systems cyclic triaxial test on the saturated reinforced clay near Shanghai Metro Line 4’s Hailun Road station. Initially, the study examines the impacts of frequency, dynamic stress amplitude (DSA), and loading cycles on cumulative plastic strain. Following this, the orthogonal design method was employed to organize tests, and an evaluation method for assessing soil strain was developed through mathematical statistical analysis. The results indicate at the constant vibration frequency, cumulative plastic strain increases with an increase in DSA and decreases with as load frequency increases. DSA is the primary factor influencing the axial deformation of subway tunnels, whereas the interaction between load frequency and vibration frequency is negligible. The findings suggest that measures to prevent and control subway tunnel settlement should concentrate on DSA during the early stages of subway operation.

Investigation of vibration of nanorotating plates submerged in viscous-moving fluid medium

ABSTRACT In view of the great importance of dynamical behavior prediction of nanostructures in the fluid media and their various applications in biomedical engineering, aerospace, etc. in this research, the free vibration behavior of a nano-scale rotating plate coupled with an incompressible viscous fluid is studied. To this end, nonlocal elasticity theory is adopted to apply small-scale effects. Using the Navier–Stokes relation, the interaction forces between the fluid and nanorotating plate are obtained. In order to solve the governing differential equations, the Galerkin method is utilized, and the system’s vibration frequency response has been obtained for the clamped-free-free-free boundary condition.

Multiscale analysis of carbon nanotube-reinforced curved beams: A finite element approach coupled with multilayer perceptron neural network

This paper presents a comprehensive investigation into the structural response of curved composite beams enhanced with carbon nanotube (CNT). Employing a multiscale framework, our analysis leverages the finite element method (FEM) to account for both bending and shear deformations across six degrees of freedom. The inquiry encompasses diverse mechanical, geometrical, and boundary configurations to assess these composite beams' natural vibration features. Moreover, we introduce a multilayer perceptron (MLP) neural network architecture designed to forecast such beams' dimensionless first natural frequency. Trained on a meticulously curated dataset derived from FEM simulations, the neural network model exhibits promising predictive capabilities concerning the free vibration frequency. To ascertain the efficacy and precision of our proposed methodology, we conduct a comparative analysis between FEM results and employ statistical metrics to evaluate the neural network's predictive performance. The findings of this study reveal an impressive predictive accuracy of over 95 % with regards to the initial natural frequency of the composite beams, thereby emphasizing the potential effectiveness of neural network methodologies in engineering analyses. This study significantly contributes to advancing our comprehension of the vibrational dynamics inherent in carbon nanotube-reinforced composite beams, while concurrently underscoring the potential efficacy of neural networks in forecasting their dynamic attributes.

Solving the puzzle of the carbonic acid vibrational spectrum - An anharmonic story.

Against the general belief that carbonic acid is too unstable for synthesis, it was possible to synthesize the solidas well as gas-phase carbonic acid.It was suggested that solid carbonic acid might exist in Earth's upper troposphere and in the harsh environments of other solar bodies,where it undergoes a cycle of synthesis, decomposition, and dimerization.To provide spectroscopic data for probing the existence of extraterrestrial carbonic acid,matrix-isolation infrared (MI-IR) spectroscopy has shown to be essential.However, early assignments within the harmonic approximation using scaling factors impeded a full interpretation of the rather complex MI-IR spectrum of H2CO3. Recently, carbonic acid was detected in the Galactic center molecular cloud and triggered new interest in the anharmonic spectrum.In this regard, we substantially reassign our Argon MI-IR spectra relying on accurate anharmonic calculations. We calculate a four-mode potential energy surface (PES) at the explicitly correlated coupled-cluster theory using up to triple-zeta basis sets, i.e., CCSD(T)-F12/cc-pVTZ-F12. On this PES, we perform vibrational self-consistent field and configuration interaction (VSCF/VCI) calculations to obtain accurate vibrational transition frequencies and resonance analysis of the fundamentals, first overtones, and combination bands.

Solvent Effect on Dative and Ionic Bond Strengths: A Unified Theory from the Potential Analysis and Valence Bond (VB) Computation.

Solvent molecules interact with a solute through various intermolecular forces. Here we employed a potential energy surface (PES) analysis to interpret the solvent-induced variations in the strengths of dative (Me3NBH3) and ionic (LiCl) bonds, which possess both ionic and covalent (neutral) characteristics. The change of a bond is driven by the gradient (force) of the solvent-solute interaction energy with respect to the focused bond length. Positive force shortens the bond length and increases the bond force constant, leading to a blue-shift of the bond stretching vibrational frequency upon solvation. Conversely, negative force elongates the bond, resulting in a reduced bond force constant and red-shift of the stretching vibrational frequency. The different responses of Me3NBH3 and LiCl to solvation are studied with valence bond (VB) theory, as Me3NBH3 and LiCl are dominated by the neutral covalent VB structure and the ionic VB structure, respectively. The dipole moment of an ionic VB structure increases along the increasing bond distance, while the dipole moment of a neutral covalent VB structure increases with the decreasing bond distance. The roles of the dominating VB structures are further examined by the geometry optimizations and frequency calculations with the block-localized wavefunction (BLW) method.

Multi-condition adaptive detail characterization model of magnetorheological dampers and experimental verification

The theoretical model for predicting the damping characteristics of magnetorheological dampers (MRDs) is significant for enhancing the design efficiency of the control algorithm. However, some existing theoretical models face limitations in characterizing MRD damping characteristics simultaneously in terms of nonlinear detail characterization and adaptability to variable working conditions. Therefore, this paper proposed the Composite Double-Boltzmann (CDB) model combining the Double-Boltzmann (DB) function widely used in the field of biology and chemistry for its strong nonlinear characterization capability. Utilizing this model to fit the sinusoidal vibration testing data of the MRD prototype under variable combination working conditions, obtaining quantitative relationships between the undetermined parameters in the CDB model and the excitation current, vibration frequency, and amplitude to enable the model to address both the nonlinear details characterization of MRDs and adaptability to variable working conditions. Subsequently, the validity of the quantitative relationships were verified by comparing the calculated parameter values using the quantitative relationships with the original accurate parameter values. In order to verify the validity of the CDB model, extensive unknown working condition vibration tests were conducted on the MRD prototype under variable excitation currents, vibration frequencies, amplitudes and random excitation working conditions, employing the CDB and Tanh models to predict the damping characteristics, to compare to demonstrate the CDB model’s capability of adapting to variable working conditions while accurately characterizing the nonlinear details of MRD damping characteristics.

Measurement of high-frequency speckle vibration amplitude from a blurred image

The non-contact detection of a vibrating surface through the extraction of the vibration of the speckle pattern that the surface produces when illuminated by a coherent source of light has been implemented almost from the invention of the laser and is still an active field of research. In this work, the vibration amplitude of a speckle pattern is measured using a single blurred image taken with exposure times that are multiples of the vibration period. The method is based on the variation of the cross-correlation function width as a function of the speckle vibration amplitude. There is no analytical expression for that function, so it must be obtained numerically. The oscillating speckle patterns were produced with a piezoelectric transducer excited at vibration frequencies ranging from a few Hz up to tens of kHz. A custom CMOS photodetector sensor with programmable interconnection between pixels was used to verify the speckle pattern vibration amplitude and frequency.

Dynamic Analysis of 2D FG Porous Thick Cylindrical Shells Under Thermal Shock

In this research, a thick hollow cylindrical shell made of bidirectional functionally graded open cell porous materials under internal thermal shock according to the classical theory of linear thermo-elasticity is examined for the first time. The cylinder is made of a porous cellular material and its porosity varies along both radial and axial directions continuously. The governing motion equations are obtained by using 2D-axisymmetric theory of linear thermo-elasticity rather than shell theories. This theory represents thickness stretching and gives more precise results. Graded finite element method is employed to model the problem. Applying this method rather than conventional FEM leads to more accurate results, especially for dynamic analyses. The cubic higher order element is used for dividing the solution domain. To obtain transient temperatures, Crank–Nicolson algorithm is used and then the Newmark procedure is used to derive time responses of displacement and stress components. The time history of displacements and stress components for different radial and axial power law exponents, porosity coefficient, boundary conditions, length-to-thickness ratio and two different porosity patterns are investigated in detail. The obtained results show that thermal-induced vibration is generally caused by hoop stress, and frequency and amplitude of vibrations and velocity of stress waves are considerably influenced by the porosity distribution, porosity coefficient and power law exponents in both directions.

Synthesis, characterization and structure-property relations in mullite-type Pb2(Pb1−x Sn x )O4 solid solution

Abstract The crystal structures of both Pb2PbO4 (Pb3O4) and Pb2SnO4 at room temperature can be described using mullite-type setting in the space groups P42/mbc and Pbam, respectively. At what chemical extend the crystal structure prefers either of the space groups would be an excellent playground in the Pb2(Pb1−x Sn x )O4 solid solution. Members of the solid solutions have been prepared by solid-state reactions carried out in sealed quartz tubes. Each sample has been found to be phase pure confirmed by X-ray powder diffraction data Rietveld refinement. Samples with higher tin content require higher synthesis temperatures, and controlled decomposition of Pb3O4 serves as the source for both Pb2+ and Pb4+ cations. Since the Pb4+ cation is larger than Sn4+, the MO6 polyhedral volume decreases with increasing Sn-content. As such, each metric parameter shows a linear trend following Vegard’s rule. The concomitant contraction of the MO6 octahedra and the high stereo-chemical activity of the 6s 2 lone electron pairs of lead in the Pb2+O4 distorted pyramid results in symmetry reduction. DFT suggests dynamical instability of the tetragonal Pb3O4 while Pb2SnO4 keeps orthorhombic symmetry at low temperatures, which agrees well with the experimental findings. The global blue shift of the vibrational mode frequencies is explained by the quasi-harmonic approach. The indirect band-gap linearly increases from 2.1(1) eV (x = 0) to a maximum value of 2.5(1) eV for x = 0.8 followed by a sharp drop towards Pb2SnO4. Thermogravimetric analysis demonstrates higher thermal stability with increasing Sn-content, which is explained in terms of higher bond strength of Sn–O than that of Pb–O in the MO6 octahedra.

Development of a Prototype Hydraulic Damping Device for Hot Water Heating Circuit in Pulse Mode

This paper provides a comprehensive exploration into the design and implementation of the hydraulic damping device within a pulse mode hot water heating loop. It outlines a systematic approach aimed at optimizing system performance, detailing the operational principles of the pulse mode heating circuit and presenting a structured construction scheme for the hydraulic damping apparatus. Accompanying this analysis is a simplified diagram illustrating the hydraulic damping system, offering a clear visual representation of its integration within the heating circuit. Through mathematical transformations, essential parameters such as complex impedance, frequency function, and vibration frequency characteristics are derived, providing valuable insights into the dynamic behavior of the system. Culminating this investigation, the paper constructs the frequency response of the circuit, offering a comprehensive understanding of its dynamic behavior across varying frequencies. This synthesis of theoretical frameworks and practical applications advances our understanding of pulse mode hot water heating technology, paving the way for enhanced efficiency and performance in heating systems.

Measuring the Electric Fields of Ions Captured in Crown Ethers.

Controlling reactivity with electric fields is a persistent challenge in chemistry. One approach is to tether ions at well-defined locations near a reactive center. To quantify fields arising from ions, we report crown ethers that capture metal cations as field sources and a covalently bound vibrational Stark shift probe as a field sensor. We use experiments and computations in both the gas and liquid phases to quantify the vibrational frequencies of the probe and estimate the electric fields from the captured ions. Cations, in general, blue shift the probe frequency, with effective fields estimated to vary in the range of ∼0.2-3 V/nm in the liquid phase. Comparison of the gas and liquid phase data provides insight into the effects of mutual polarization of the molecule and solvent and screening of the ion's field. These findings reveal the roles of charge, local screening, and geometry in the design of tailored electric fields.

Design and Control of the Natural Frequency of Brake Discs in the Aspect of the Gray Cast Iron Production Process

The results of research on the influence of the chemical composition of cast iron and its potential changes in the production cycle on the elastic properties and the correctness of numerical simulations of the natural frequency of ventilated brake discs are presented. The tests were carried out for three grades of gray cast iron with flake graphite with a eutectic saturation coefficient ranging from 0.88 to 1.01. A quantitative metallographic assessment of the pearlitic cast iron matrix and graphite precipitates was carried out, and the hardness and compressive/tensile strength of individual cast iron grades were determined, taking into account the limit contents of the alloying elements. Next, ultrasonic tests were performed, and the elastic properties of cast iron were determined. Based on the obtained data, a numerical modal analysis of brake discs was performed, the results of which were compared with the actual values of an FRF frequency analysis. The error of the computer simulations was estimated at approx. 1%, and it was found that the accuracy of the calculations of the first natural frequency did not depend on the dimensions (size) of the discs and the chemical composition of the cast iron from which they were cast. The functional relationships between the chemical composition of cast iron, its strength and elasticity and the first natural frequency of the disc vibrations were determined, and a database of the material parameters of the produced cast iron grades was developed. An implementation example showed the validation of the brake disc design with natural frequency prediction and demonstrated a high convergence of the experimental results with the simulated values. Using I-MR control cards, both the effectiveness of designing and predicting the natural vibrations of brake discs based on the implemented material database as well as the stability of the gray cast iron production and disc casting processes were confirmed.

Ab Initio Study of the Graphyne-like γ-SiC Nanoflake for Toxic Gas-Sensing Applications.

This study focuses on the geometrical, electronic, and optical properties of the γ-graphyne-like novel γ-SiC nanoflake of the γ-silicon carbide (SiC) monolayer using density functional theory calculations. γ-SiC was revealed to be a stable semiconducting nanoflake confirmed by a negative cohesive energy, real vibrational frequencies, and a 1.749 eV energy gap. The adsorption of COCl2, HCN, PH3, AsH3, CNCl, and C2N2 toxic gases on the γ-SiC nanoflake is also studied, which revealed an attractive gas-nanoflake interaction with the adsorption energy ranging from -0.21 to -0.38 eV. The adsorption results in a significant charge transfer between gas-adsorbent complexes. A significant variation in the energy gap and electrical conductivity was observed due to gas adsorption. γ-SiC showed maximum sensitivity at room temperature for CNCl gas. The entire process of adsorption is exothermic and thermodynamically stable. γ-SiC showed a high absorption coefficient over 104 orders with a significant variation in the absorption peak intensity and blue peak shifting. According to the quantum theory and reduced density gradient analysis, all of the gases are physisorbed on the γ-SiC nanoflake due to van der Waals interactions. The obtained results signify the usability of γ-SiC as a potential toxic gas sensor.

Effect of high-intensity vibration parameter on droplet transport characteristics in gas channel of proton exchange membrane fuel cell

In aerospace applications, proton exchange membrane fuel cells are subject to high-intensity vibration. Vibration has a substantial effect on water transport in fuel cells. However, there is a lack of research on the effects of multi-directional and high-intensity vibration conditions on fuel cells. In this study, the droplet transport characteristics in the gas channel under high-intensity vibration conditions are investigated for the first time. Moreover, the effects of vibration direction and vibration frequency on the droplet dynamic transport process are specifically studied. The droplet transport state, drainage performance, and pressure drop variation in the gas channel under different vibration conditions are analyzed and interpreted. The results show that low-frequency vibration in the longitudinal direction is more conducive to the droplet discharge, and the pressure drop undergoes a periodic change corresponding to the vibration frequency. Vertical vibration promotes droplet detachment from the gas diffusion layer surface, which contributes to the reduction in water coverage ratio on its surface, despite an increase in the channel pressure drop. Under the influence of horizontal vibration, droplets are more susceptible to adsorption on the channel sidewalls and turn into a liquid film, which leads to a longer discharge time and a reduction in pressure drop.

Statistics of kinetic and thermal energy dissipation rates in vibrational turbulent Rayleigh–Bénard convection with rough surface

In this paper, the statistical properties of the kinetic εu and thermal εθ dissipation rates in two-dimensional (2D) turbulent Rayleigh–Bénard convection (RBC) are studied by using the thermal lattice Boltzmann method (LBM). A series of direct numerical simulations (DNS) are implemented in a square cell with the unit aspect ratio for the Rayleigh number Ra = 108 and Prandtl number Pr = 4.38. The roughness height h* and vary the vibration frequency ω* from 0 to 1000 are fixed in the vibrational RBC with rough plates to explore their effect on the kinetic and thermal dissipation rates. The global features indicate that the εu and εθ are more intense in the regions with high gradients of velocity and temperature, which is in good agreement with the previous work. The scalings of Nu∼ω *0.55±0.1 and Re∼0.59±0.2 are proposed between the ensemble averaged Nusselt number Nu and Reynolds number Re. The probability density functions (PDFs) of both logarithmic kinetic dissipation rate lg εu and thermal dissipation rate lg εθ are not conformed to the log-normal distributions. Through the analysis of the time-averaged εu and εθ vertical profiles, it is further demonstrated that the local dissipation rates from the boundary layer region are still the major contribution in the vibrational RBC with rough plates.