Geometrical structures, vibrational frequencies, force constants and dissociation energies of isotopic water molecules (H_2O, HDO, D_2O, HTO, DTO, and T_2O) under dipole electric field

The dissociation limits of isotopic water molecules are derived for the ground state. The equilibrium geometries, the vibrational frequencies, the force constants and the dissociation energies for the ground states of all isotopic water molecules under the dipole electric fields from -0.05 a.u. to 0.05 a.u. are calculated using B3P86/6-311＋＋G（3df,3pf）. The results show that when the dipole electric fields change from -0.05 a.u. to 0.05 a.u., the bond length of H-O increases whereas the bond angle of H-O H decreases because of the charge transfer induced by the applied dipole electric field. The vibrational frequencies and the force constants of isotopic water molecules change under the influence of the strong external torque. The dissociation energies increase when the dipole electric fields change from -0.05 a.u. to 0.05 a.u. and the increased dissociation energies are in the order of H2O, HDO, HTO, D2O, DTO, and T2O under the same external electric fields.

Structures,Electron Affinities and Vibrational Frequencies of SF_5OX/SF_5OX^-(X=F,Cl,Br)

The molecular structures,electron affinities,vibrational frequencies and IR intensities of the SF5OX/SF5OX-（X=F,Cl,Br）species have been determined by four different density functional theory（DFT）methods（B3LYP,BHLYP,BP86,BLYP）in conjunction with DZP＋＋ basis set.The BHLYP method predicts the best geometry parameters.The adiabatic electron affinities（EAad）predicted by the B3LYP/DZP＋＋ method are 4.36 eV（SF5OF）,4.13 eV（SF5OCl）,4.12 eV（SF5OBr）,respectively.Large electron affinity implies the corresponding anions are stable.The total intensities in the near IR ＂window＂ of the anions SF5OX-（X=F,Cl,Br）at B3LYP level are 1 602 km/mol（SF5OF-）,1 868 km/mol（SF5OCl-）and 1 916 km/mol（SF5OBr-）,respectively,larger than those of the corresponding neutrals.It suggests that SF5OX/SF5OX-（X=F,Cl,Br）may be used to ＂warm＂ Mars.

Ab initio study of vibrational frequencies, force field and normal coordinate analysis of the cis- and trans-isomers of nitrosomethanol

In this paper, the equilibrium geometries of two isomers of the newly found compound ——nitrosomethanol——have been optimized by ab initio SCF MO method with 3-21G basic set by gradient technique. And the second derivatives of potential energy (i. e. the force constant matrix elements) have been calculated analytically. Hence the entire force fields of the two isomers of nitro- somethanol have been obtained theoretically. The theoretical vibrational frequencies and the corres- ponding normal modes were obtained and compared with the experimental values. and the structures of two isomeric forms of nitrosomethanol are established.

Research on modeling and self-excited vibration mechanism in magnetic levitation-collision interface coupling system

The modeling and self-excited vibration mechanism in the magnetic levitation-collision interface coupling system are investigated.The effects of the control and interface parameters on the system's stability are analyzed.The frequency range of self-excited vibrations is investigated from the energy point of view.The phenomenon of self-excited vibrations is elaborated with the phase trajectory.The corresponding control strategies are briefly analyzed with respect to the vibration mechanism.The results show that when the levitation objects collide with the mechanical interface,the system's vibration frequency becomes larger with the decrease in the collision gap;when the vibration frequency exceeds the critical frequency,the electromagnetic system continues to provide energy to the system,and the collision interface continuously dissipates energy so that the system enters the self-excited vibration state.

Ab initio potential energy surface and anharmonic vibration spectrum of NF_(3)^(+)

Potential energy surfaces(PESs), vibrational frequencies, and infrared spectra are calculated for NF_(3)^(+) using ab initio calculations, based on UCCSD(T)/cc-p VTZ combined with vibrational configuration interaction(VCI). Based on an iterative algorithm, the surfaces(SURF) program adds automatic points to the lattice representation of the potential function, the one-dimensional and two-dimensional PESs are calculated after reaching a convergence threshold, finally the smooth image of the potential energy surface is fitted. The PESs accurately account for the interaction between the different modes, with the mode q_(6) symmetrical stretching vibrations having the greatest effect on the potential energy change of the whole system throughout the potential energy surface shift. The anharmonic frequencies are obtained when the VCI matrix is diagonalized. Fundamental frequencies, overtones, and combination bands of NF_(3)^(+) are calculated, which generate the degenerate phenomenon between their frequencies. Finally, the calculated anharmonic frequency is used to plot the infrared spectra.Modal antisymmetric stretching ν_(5) and symmetric stretching ν_(6) exhibit a phenomenon of large-intensity borrowing. This study can provide data to support the characterization in the laboratory.

A critical review of wheel/rail high frequency vibration-induced vibration fatigue of railway bogie in China

Purpose–This review aims to give a critical view of the wheel/rail high frequency vibration-induced vibration fatigue in railway bogie.Design/methodology/approach–Vibration fatigue of railway bogie arising from the wheel/rail high frequency vibration has become the main concern of railway operators.Previous reviews usually focused on the formation mechanism of wheel/rail high frequency vibration.This paper thus gives a critical review of the vibration fatigue of railway bogie owing to the short-pitch irregularities-induced high frequency vibration,including a brief introduction of short-pitch irregularities,associated high frequency vibration in railway bogie,typical vibration fatigue failure cases of railway bogie and methodologies used for the assessment of vibration fatigue and research gaps.Findings–The results showed that the resulting excitation frequencies of short-pitch irregularity vary substantially due to different track types and formation mechanisms.The axle box-mounted components are much more vulnerable to vibration fatigue compared with other components.The wheel polygonal wear and rail corrugation-induced high frequency vibration is the main driving force of fatigue failure,and the fatigue crack usually initiates from the defect of the weld seam.Vibration spectrum for attachments of railway bogie defined in the standard underestimates the vibration level arising from the short-pitch irregularities.The current investigations on vibration fatigue mainly focus on the methods to improve the accuracy of fatigue damage assessment,and a systematical design method for vibration fatigue remains a huge gap to improve the survival probability when the rail vehicle is subjected to vibration fatigue.Originality/value–The research can facilitate the development of a new methodology to improve the fatigue life of railway vehicles when subjected to wheel/rail high frequency vibration.

Methanol Perturbing Modeling Cell Membranes Investigated using Linear and Nonlinear Vibrational Spectroscopy

Cell membranes play a crucial role in many biological functions of cells. A small change in the composition of cell membranes can strongly influence the functions of membrane-associated proteins, such as ion and water channels, and thus mediate the chemical and physical balance in cells. Such composition change could originate from the introduction of short-chain alcohols, or other anesthetics into membranes. In this work, we have applied sum frequency generation vibrational spectroscopy （SFG-VS）, supplemented by attenuated total reflectance Fourier transform infrared spectroscopy （ATR-FTIR）, to investigate interaction between methanol and 1,2-dimyristoyl-d54-sn-glycero-3-phosphocholine （d54-DMPC） lipid bilayers. Lipid＇s hydrocarbon interior is deuterated while its head group is hydrogenated. At the same time, CH3 symmetric stretch from methanol and lipid head amine group has different frequency, thus we can distinguish the behaviors of methanol, lipid head amine group, and lipid hydrocarbon interior. Based on the spectral feature of the bending mode of the water molecules replaced by methanol, we determined that the methanol molecules are intercalated into the region between amine and phosphate groups at the lipid hydrophilic head. The dipole of CH3 groups of methanol and lipid head, and the water O-H M1 adopt the same orientation directions. The introduction of methanol into the lipid hydrophilic head group can strongly perturb the entire length of the alkyl chains, resulting that the signals of CD2 and CD3 groups from both leaflets can not cancel each other.

Methanol Adsorption on TiO2 Film Studied by Sum Frequency Generation Vibrational Spectroscopy

A broadband infrared surface sum frequency generation vibrational spectroscopy （SFG-VS） and an in situ UV excitation setup devoted to studying surface photocatalysis have been constructed. With a home-made compact high vacuum cell, organic contaminants on TiO2 thin film surface prepared by RF magnetron sputtering were in situ removed under 266 nm irradiation in 10 kPa 02 atmosphere. We obtained the methanol spectrum in the CH3 stretching vibration region on TiO2 surface with changing the methanol pressure at room temperature. Features of both molecular and dissociative methanol, methoxy, adsorbed on this surface were resolved. The CH3 symmetric stretching vibration frequency and Fermi resonance of molecular methanol is red-shifted by about 6-8 cm-1 from low to high coverage. Moreover, the recombination of dissociative methanol and H on Surfaces in vacuum was also observed. Our results suggest two equilibria exist： between molecular methanol in the gas phase and that on surfaces, and between molecular methanol and dissociative methanol on surfaces.

Influence of mortar gap on natural vibration frequencies of high-speed railway track-bridge system

Based on Hamilton’s principle, the differential equations of free vibration of track-bridge systems with mortar gap are derived. Hence, a method for calculating the natural frequencies of track-bridge systems is proposed. The influence of the flexural stiffness of the track-bridge system, the vertical and longitudinal stiffness of the mortar layer,gap position and gap length on the natural frequencies of a track-bridge system is discussed. The results show that the natural frequencies of the track-bridge system are more sensitive to the change of the flexural stiffness of the bridge layer. The change of the longitudinal stiffness of the mortar layer and gap position has no obvious effect on the trackbridge system’s natural frequencies, while the interlayer vertical stiffness has a larger impact. The gap length has a more significant effect on the 4th-5th order natural frequencies of the track-bridge system. The range of the natural frequencies that are affected by the gap widens as the gap length increases.

A Highly Sensitive Femtosecond Time-Resolved Sum Frequency Generation Vibrational Spectroscopy System with Simultaneous Measurement of Multiple Polarization Combinations

Characterization of real-time and ultrafast motions of the complex molecules at surface and interface is critical to understand how interracial molecules function. It requires to develop surface-sensitive, fast-identification, and time-resolved techniques. In this study, we employ several key technical procedures and successfully develop a highly sensitive femtosecond time-resolved sum frequency generation vibrational spectroscopy （SFG-VS） system. This system is able to measure the spectra with two polarization combinations （ssp and ppp, or psp and ssp） simultaneously. It takes less than several seconds to collect one spectrum. To the best of our knowledge, it is the fastest speed of collecting SFG spectra reported by now. Using the time-resolved measurement, ultrafast vibrational dynamics of the N-H mode of α-helical peptide at water interface is determined. It is found that the membrane environment does not affect the N-H vibrational relaxation dynamics. It is expected that the time-resolved SFG system will play a vital role in the deep understanding of the dynamics and interaction of the complex molecules at surface and interface. Our method may also provide an important technical proposal for the people who plan to develop time-resolved SFG systems with simultaneous measurement of multiple polarization combinations.

Calculations of the vibrational frequency and isotopic shift of UF_6 and U_2 F_6

Molecular structure, vibrational frequency and infrared intensity of UF6 are investigated by using the revised Perdew Burke-Enzerhof function with the triple-zeta polarized basis set. The calculation results are in good agreement with the experimental values and indicate the existence of a stable U2F6 molecule with a multiple bonded U2 unit. The calculation results also predict that the D3d symmetry of U2F6 is more stable than D3h. The optimized geometries, vibrational frequencies, and infrared intensities are also reported for U2F6 molecules in D3d symmetry. In addition, the isotopic shift of vibrational frequencies of the two molecules under isotopic substitution of uranium atom are also investigated with the same method. The U2F6 molecule is predicted to be better than UF6 for laser uranic isotope separation.

The Effect of Cutout on Natural Frequencies of Thin Plate

The laws that natural frequencies of rectangular plate with a cutout will change with size and position of cutout are obtained by analytic, numerical and experimental methods.

Structures and Vibrational Spectra of C_(2) and LaC^(+)_(2) Clusters

C 2 and LaC + 2 were studied using Hartree Fock(HF), B3LYP (Becke 3 paremeter Lee Yang Parr) density functional method, second order Mφller Plesset perturbation(MP2) and coupled cluster singles and doubles with non iterative triples(CCSD(T)) methods. The basis set employed was LANL1DZ. Geometries, vibrational frequencies and other quantities were reported. The results showed that for C 2, all the methods performed well for low spin state(singlet), while only HF and B3LYP remained so for high spin state(triplet). For LaC + 2, four isomers were presented and fully optimized. The results suggested that linear isomers with C ∞v and D ∞h symmetries were predicted to be saddle points on the energy surface for all the methods, while for isomers with C 2v and C s symmetries, they were local minima except C 2v at B3LYP level, and were isoenergetic at HF, MP2 and CCSD(T) levels, near isoenergetic at B3LYP level. From the differences between HOMO and LUMO, it is also known that the isomers with C 2v and C s symmetries offer the largest values and therefore correspond to the most stable structure. For La—C bond lengths, B3LYP gives the shortest, the order is B3LYP<HF<MP2<CCSD(T) for all the methods.

Structural, electronic and vibrational properties of indium oxide clusters

Geometric, electronic and vibrational properties of the most stable and energetically favourable configurations of indium oxide clusters InmOn （1 ≤m, n ≤ 4） are investigated using density functional theory. The lowest energy geometries prefer the planar arrangement of the constituent atoms with a trend to maximize the number of ionic In-O bonds. Due to the charge transfer from In to O atoms, the electrostatic repulsion occurs between the atoms with the same kind of charge. The minimization of electrostatic repulsion and the maximization of In O bond number compete between each other and determine the location of the isometric total energy. The most stable linear In-O-In-O structure of In2O2 cluster is attributed to the reduced electrostatic repulsive energy at the expense of In-O bond number, while the lowest energy rhombus-like structure of In2O3 cluster reflects the maximized number of In O bonds. Furthermore, the vibrational frequencies of the lowest energy clusters are calculated and compared with the available experimental results. The energy gap and the charge density distribution for clusters with varying oxygen/indium ratio are also discussed.

Vibrational Spectra and Adsorption of Trisiloxane Superspreading Surfactant at Air/Water Interface Studied with Sum Frequency Generation Vibrational Spectroscopy

The C-H stretch vibrational spectra of the trisiloxane superspreading surfactant Silwet L-77 （（CH3）3Si- O-Si（CH3）（C3H6）（OCH2CH2）7-8OCH3）-O-Si（CH3）3） at the air/water interface are measured with the surface Sum Frequency Generation Vibrational Spectroscopy （SFG-VS）. The spectra are dominated with the features from the -Si-CH3 groups around 2905 cm^-1 （symmetric stretch or SS mode） and 2957 ^-1 （mostly the asymmetric stretch or AS mode）, and with the weak but apparent contribution from the -O-CH2- groups around 2880 ^-1 （symmetric stretch or SS mode）. Comparison of the polarization dependent SFG spectra below and above the critical aggregate or micelle concentration （CAC） indicates that the molecular orientation of the C-H related molecular groups remained unchanged at different surface densities of the Silwet L-77 surfactant. The SFG-VS adsorption isotherm suggested that there was no sign of Silwet L-77 bilayer structure formation at the air/water interface. The Gibbs adsorption free energy of the Silwet surfactant to the air/water interface is -42.2±0.8kcal/mol, indicating the unusually strong adsorption ability of the Silwet L-77 superspreading surfactant.

Sum Frequency Generation Vibrational Spectra of Perovskite Nanocrystals at the Single-Nanocrystal and Ensemble Levels

Determination of molecular structures of organicinorganic hybrid perovskite(OIHP)nanocrystals at the single-nanocrystal and ensemble levels is essential to understanding the mechanisms responsible for their size-dependent optoelectronic properties and the nanocrystal assembling process,but its detection is still a bit challenging.In this study,we demonstrate that femtosecond sum frequency generation(SFG)vibrational spectroscopy can provide a highly sensitive tool for probing the molecular structures of nanocrystals with a size comparable to the Bohr diameter(∼10 nm)at the single-nanocrystal level.The SFG signals are monitored using the spectral features of the phenyl group in(RMBA)PbBr_(3) and(R-MBA)_(2)PbI_(4) nanocrystals(MBA:methyl-benzyl-ammonium).It is found that the SFG spectra exhibit a strong resonant peak at 3067±3 cm^(−1)(ν2 mode)and a weak shoulder peak at 3045±4 cm^(−1)(ν_(7a) mode)at the ensemble level,whereas a peak of theν2 mode and a peak at 3025±3 cm^(−1)(ν20b mode)at the single-nanocrystal level.The nanocrystals at the single-nanocrystal level tend to lie down on the surface,but stand up as the ensemble number and the averaged sizes increase.This finding may provide valuable information on the structural origins for size-dependent photo-physical properties and photoluminescence blinking dynamics in nanocrystals.

Absolute Orientation of Molecules with Competing Hydrophilic Head Groups at the Air/Water Interface Probed with Sum Frequency Generation Vibrational Spectroscopy

The constructive or destructive spectral interference between the molecular groups oriented up and down at the interface in the sum-frequency generation （SFG） spectra provides a direct measurement of the absolute orientation of these molecular groups. This simple approach can be employed to interrogate absolute molecular orientations other than using the complex absolute phase measurement in the SFG studies. We used the -CN group in the p-cyanophenol （PCP） molecule as the internal phase standard, and we measured the phases of the SFG fields of the -CN groups in the 3,5-dimethyl-4-hydroxy-benzonitrile （35DMHBN） and 2,6-dimethyl-4-hydroxy-benzonitrile （26DMHBN） at the air/water interface by measuring the SFG spectra of the aqueous surfaces of the mixtures of the PCP, 35DMHBN, and 26DMHBN solutions. The results showed that the 35DMHBN had its -CN group pointing into the aqueous phase; while the 26DMHBN, similar to the PCP, had its -CN group pointing away from the aqueous phase. The tilt angles of the -CN group for both the 35DMHBN and 26DMHBN molecules at the air/water interface were around 25°-45° from the interface normal. These results provided insights on the understanding of the detailed balance of the competing factors, such as solvation of the polar head groups, hydrogen bonding and hydrophobic effects, etc., on influencing the absolute molecular orientation at the air/water interface.

Experimental research and energy analysis of a new type of dry ice powder pneumatic rock breaking technology

When the traditional drill and blast method is applied to rock crushing projects,it has strong vibration,loud noise and dust pollution,so it cannot be used in densely populated areas such as urban public works.We developed a supercritical CO_(2)true triaxial pneumatic rock-breaking experimental system,and conducted laboratory and field tests of dry ice powder pneumatic rock-breaking.The characteristics of the blast-induced vibration velocity waveform and the evolution of the vibration velocity and frequency with the focal distance were analyzed and discussed.The fracturing mechanism of dry ice powder pneumatic rock breaking is studied.The research results show that:(1)The vibration velocity induced by dry ice powder pneumatic rock breaking decays as a power function with the increase of the focal distance;(2)The vibration frequency caused by dry ice powder pneumatic rock breaking is mainly distributed in 1–120 Hz.Due to the dispersion effect,the dominant frequency of 10–30 Hz appears abnormally attenuated;(3)The traditional CO_(2)phase change fracturing energy calculation formula is also applicable to dry ice pneumatic rock breaking technology,and the trinitrotoluene(TNT)equivalent of fracturing energy is applicable to the Sadovsky formula;(4)Dry ice powder pneumatic rock breaking is shock wave and highenergy gas acting together to fracture rock,which can be divided into three stages,among which the gas wedge action of high-energy gas plays a dominant role in rock mass damage.

A high frequency vibration compensation approach for ultrahigh resolution SAR imaging based on sinusoidal frequency modulation Fourier-Bessel transform

Ultrahigh resolution synthetic aperture radar(SAR)imaging for ship targets is significant in SAR imaging,but it suffers from high frequency vibration of the platform,which will induce defocus into SAR imaging results.In this paper,a novel compensation method based on the sinusoidal frequency modulation Fourier-Bessel transform(SFMFBT)is proposed,it can estimate the vibration errors,and the phase shift ambiguity can be avoided via extracting the time frequency ridge consequently.By constructing the corresponding compensation function and combined with the inverse SAR(ISAR)technique,well-focused imaging results can be obtained.The simulation imaging results of ship targets demonstrate the validity of the proposed approach.

Safety Assessment of Liquid Launch Vehicle Structures Based on Interpretable Belief Rule Base

A liquid launch vehicle is an important carrier in aviation,and its regular operation is essential to maintain space security.In the safety assessment of fluid launch vehicle body structure,it is necessary to ensure that the assessmentmodel can learn self-response rules from various uncertain data and not differently to provide a traceable and interpretable assessment process.Therefore,a belief rule base with interpretability(BRB-i)assessment method of liquid launch vehicle structure safety status combines data and knowledge.Moreover,an innovative whale optimization algorithm with interpretable constraints is proposed.The experiments are carried out based on the liquid launch vehicle safety experiment platform,and the information on the safety status of the liquid launch vehicle is obtained by monitoring the detection indicators under the simulation platform.The MSEs of the proposed model are 3.8000e-03,1.3000e-03,2.1000e-03,and 1.8936e-04 for 25%,45%,65%,and 84%of the training samples,respectively.It can be seen that the proposed model also shows a better ability to handle small sample data.Meanwhile,the belief distribution of the BRB-i model output has a high fitting trend with the belief distribution of the expert knowledge settings,which indicates the interpretability of the BRB-i model.Experimental results show that,compared with other methods,the BRB-i model guarantees the model’s interpretability and the high precision of experimental results.