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.

Coherent Vibrational Dynamics and High-resolution Nonlinear Spectroscopy： A Comparison with the Air/DMSO Liquid Interface

We present a comparative study on the C-H stretching vibrations at air/DMSO （dimethyl sulfoxide） interface with both the free-induction decay （FID） coherent vibrational dynamics and the sub-wavenumber high resolution sum-frequency generation vibrational spectroscopy measurements. In principle the frequency-domain and time-domain spectroscopic measurements should generate identical information for a given molecular system. However, when the molecular systems are with several coupled or overlapping vibrational modes, obtain- ing detailed spectroscopic and coherent dynamics information is not as straightforward and rather difficult from either the time-domain or the frequency domain measurements. For the case of air/DMSO interface that is with moderately complex vibrational spectra, we show that the frequency-domain measurement with sub-wavenumber high-resolution sum-frequency generation vibrational spectroscopy is probably more advantageous than the time- domain measurement in obtaining quantitative understanding of the structure and coherent dynamics of the molecular interface.

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.

Parametric vibrations in offset printing units

Vibrations of offset printing presses are serious problem, which cause many difficulties while printing and impair quality of the prints. The biggest problem lies in construction of printing unit. It mainly consists of three cylinders, but two of them are in a direct contact generate undesired vibrations. Construction of the cylinders makes that stiffness of the unit varies periodically while printing. In this paper model of offset printing unit is presented. The model is described by the system of two parametric differential equations. Computer simulations of the behaviour of the printing unit have been performed. Conditions in which parametric resonance appears are also appointed here.

Determination of the Orthotropic Material Behavior of Stator Bars and of the Material Characteristics of the Space Brackets

The end windings of generators are excited to vibrations due to electromagnetic forces which can cause severe damage （especially in case of resonance） and noise. To avoid this, it is important to predict the natural frequencies and modes of the end windings with finite elements during the design process. Hence, a material model of the complete stator bar is necessary. This paper shows the development of such a material model. The composite structure of a stator bar is quite complex and makes it impossible to provide a quick calculation of the eigenvalues. That is the reason for using a suitable, homogeneously, geometry based solid model. Special attention was paid to the experimental determination of the material characteristics of the orthotropic composite space brackets. The numerical results have been evaluated against measurements. Eigenvalues, Young＇s modulus, and shear modulus have been experimentally investigated.

周边眼偏位空孔爆破设计优化研究与应用

依据已有研究对空孔效应和设置空孔时裂纹扩展规律进行探讨,发现空孔有利于裂纹贯通,对提升爆破效果有一定帮助,但也发现传统的直线型空孔布置会导致裂纹偏向,即在空孔附近转向、偏离原发展路径,影响原设计开挖轮廓。若设置偏位空孔,则可充分利用空孔效应及导向作用以提高开挖质量。对于偏位空孔在爆破中的效应,采用数值模拟研究了不同炮孔间距、空孔偏位角下的裂纹扩展规律和炮孔间贯通情况,探讨了最优偏位角度设计,并根据模拟结果对现场爆破方案进行优化,研究实际应用效果。研究结果表明:偏位空孔对爆生裂纹具有较直线空孔更明显的导向作用,主要表现在爆生裂纹尖端向空孔本身发展或被空孔裂纹引导偏向、最终主裂纹与空孔连通或在空孔范围之外主裂纹相贯通,更利于炮孔主裂纹扩展与贯通;通过提取模拟结果并测量裂纹范围,对于孔间距在60 cm及以下时,适用于周边眼爆破设计的最优偏位角为15°,在此情况下炮孔连线方向形成了与孔心连线相平行的裂纹,能显著提升贯通效果;对于优化后的福厦铁路某隧道爆破施工方案,通过振速监测及超欠挖断面扫描分析,发现周边眼起爆引起的爆破振速降低了超过50%,超欠挖值也由平均25 cm降低至15 cm以内,整体应用效果良好。该项研究可为隧道爆破减振及超欠挖控制研究提供一定参考。

电驱动偏摆式天然橡胶割胶装置设计及运动特性分析

天然橡胶是我国重要的战略物资,针对当前胶工流失严重、割胶作业难以实现机械化等问题,设计一种电驱动偏摆式割胶装置。以理论分析结合数学建模为基础进行,通过Adams与ANSYS建立传动结构的有限元模型,并阐述运动特征规律,来验证模型的构建准确性,分析传动部件在运动情况过程下的应力分布、动态特性及振动机理,为便携式割胶装置的设计以及后期改进提供参照途径。通过运动学分析,刀片摆幅、传动结构受力与理论计算值误差分别为4%和3%;在数值模拟中传动结构的最大应力出现在Y型驱动叉与刀座的连接处,XYZ三个方向面的等效应力均小于材料屈服极限,故不会发生失效与出现共振;通过试验分析,偏摆式割胶装置样机相较于传统人工割胶刀,在割胶速度、耗皮厚度以及割胶深度上的平均值相差分别为42.3%、4.3%、0.6%,其中割胶速度差异较为显著。割胶装置的理论模型分析结果与实际样机加工制造的试验情况基本符合。

U形板焊接机器人设计与运动仿真

针对船舱狭小空间U形板角焊缝焊接工况,设计了一款类轨道悬挂式移动焊接机器人。该焊接机器人由移动机器人本体、两自由度机械臂及焊炬组成,三自由度实现焊接位置调节。首先,介绍了焊接机器人的结构设计;其次,分析了U形板最小转弯半径与机器人各变量之间的参数关系,确保转弯要求;最后,利用ADAMS仿真机器人移动过程,研究多个变量对焊炬末端在Y、Z方向偏移及振动的影响。结果表明:移动过程中,焊炬在机器人中间时的焊接轨迹最易控制;夹紧轮Z向位置为24.25mm,移动过程中Z方向偏移稳定,Y、Z方向振动微小;满足结构安装前提下,应选择刚度较大的弹簧;弹簧预紧力为20N时,Y、Z方向偏移、振动均得到较大改善。

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.

Laser Linewidth and Spectral Resolution in Infrared Scanning Sum Frequency Generation Vibrational Spectroscopy System

Sum frequency generation vibrational spectroscopy （SFG-VS） is a robust technique for inter- facial investigation at molecular level. The performance of SFG-VS mostly depends on the spectral resolution of the SFG system. In this research, a simplified function was deduced to calculate the spectral resolution of picosecond SFG system and the lineshape of SFG spectra based on the Guassian shaped functions of IR beam and visible beam. The function indicates that the lineshpe of SFG spectra from nonresonant samples can be calculated by the Guassian widths of both IR beam and visible beam. And the Voigt lineshape of SFG spectra from vibrational resonant samples can be calculated by the Homogeneous broadening （Lorentzian width） and Inhomogeneous broadening （Guassian width） of vibrational modes, as well as the Guassian widths of both IR beam and visible beam. Such functions were also applied to verify the spectral resolution of the polarization-resolved and frequency-resolved picosecond SFG-VS system which was developed by our group recently. It is shown that the linewidths of IR beams that generated from current laser system are about 1.5 cm-1. The calculated spectral resolution of current picosecond IR scanning SFG-VS system is about 4.6 cm-1, which is consist with he spctral resolution shown in the spectra of cholesterol monolayer （3.5-5 cm-1）.

Cross-Propagation Sum-Frequency Generation Vibrational Spectroscopy

Here we report the theory formulation and the experiment realization of sum-frequency generation vibrational spectroscopy （SFG-VS） in the cross-propagation （XP） geometry or configuration. In the XP-SFG-VS, the visible and the infrared （IR） beams in the SFG experiment are delivered to the same location on the surface from visible and IR incident planes perpendicular to each other, avoiding the requirement to have windows or optics to be transparent to both the visible and IR frequencies. Therefore, the XP geometry is applicable to study surfaces in the enclosed vacuum or high pressure chambers with far infrared （FIR） frequencies that can directly access the metal oxide and other lower frequency surface modes, with much broader selection of visible and IR transparent window materials. The potential applications include surface science, material science, fundamental catalytic sciences, as well as low temperature molecular sciences, etc.

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.

Shape Effect of Piezoelectric Energy Harvester on Vibration Power Generation

Vibration energy harvesting is widely recognized as the useful technology for saving energy. The piezoelectric energy harvesting device is one of energy harvester and is used to operate certain types of MEMS devices. Various factors influence the energy regeneration efficiency of the lead zirconate titanate piezoelectric (PZT) devices in converting the mechanical vibration energy to the electrical energy. This paper presents the analytical and experimental evaluation of energy regeneration efficiency of PZT devices through impedance matching method and drop-weight experiments to different shape of PZT devices. The results show that the impedance matching method has increased the energy regeneration efficiency while triangular shape of PZT device produce a stable efficiency in the energy regeneration. Besides that, it becomes clear that the power, energy and subsequently efficiency of the triangular plate are higher than those of the rectangular plate under the condition of the matching impedance and the same PZT area.

Quantitative Surface Chirality Detection with Sum Frequency Generation Vibrational Spectroscopy： Twin Polarization Angle Approach

Here we report a novel twin polarization angle （TPA） approach in the quantitative chirality detection with the surface sum-frequency generation vibrational spectroscopy （SFG-VS）. Generally, the achiral contribution dominates the surface SFG-VS signal, and the pure chiral signal is usually two or three orders of magnitude smaller. Therefore, it has been difficult to make quantitative detection and analysis of the chiral contributions to the surface SFG- VS signal. In the TPA method, by varying together the polarization angles of the incoming visible light and the sum frequency signal at fixed s or p polarization of the incoming infrared beam, the polarization dependent SFG signal can give not only direct signature of the chiral contribution in the total SFG-VS signal, but also the accurate measurement of the chiral and achiral components in the surface SFG signal. The general description of the TPA method is presented and the experiment test of the TPA approach is also presented for the SFG-VS from the S- and R-limonene chiral liquid surfaces. The most accurate degree of chiral excess values thus obtained for the 2878 cm^-1 spectral peak of the S- and R-limonene liquid surfaces are （23.7±0.4）% and （-25.4±1.3）%, respectively.

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 Spectroscopy Studies on Cell Membrane Fusion Induced by Divalent Cations

Cell membrane fusion is a fundamental biological process involved in a number of cellular living functions. Regarding this, divalent cations can induce fusion of the lipid bilayers through binding and bridging of divalent cations to the charged lipids, thus leading to the cell membrane fusion. However, the elaborate mechanism of cell membrane fusion induced by divalent cations is still needed to be elucidated.Here, surface/interface sensitive sum frequency generation vibrational spectroscopy(SFG-VS) and dynamic light scattering(DLS) were applied in this research to study the responses of phospholipid monolayer to the exposure of divalent metal ions i.e.Ca^(2+)and Mg^(2+). According to the particle size distribution results measured by DLS experiments, it was found that Ca^(2+)could induce inter-vesicular fusion while Mg^(2+)could not. An octadecyltrichlorosilane self-assembled monolayer(OTS SAM)-lipid monolayer system was designed to model the cell membrane for the SFG-VS experiment. Ca^(2+)could interact with the lipid POO_(2)^(-)head groups more strongly, resulting in cell membrane fusion more easily, in comparison with Mg^(2+). No specific interaction between the two metal cations and the C=O groups was observed. However, the C=O orientations changed more after Ca^(2+)-PO2-binding than Mg^(2+)mediation on lipid monolayer. Meanwhile, Ca^(2+)could induce dehydration of the lipids(which should be related to the strong Ca^(2+)-PO_(2)^(-)interaction), leading to the reduced hindrance for cell membrane fusion.

Vibration Control Research for the 3rd Generation Synchrotron Light Source Storage Ring Mechanical Components

The 3rd generation synchrotron light source requires high level of electron beam orbit stability.Shanghai Synchrotron Radiation Facility (SSRF) is a 3rd generation light source under construction;its orbit stability requirement is up to micro or sub-micro range.The storage ring mechanical components vibration caused by the ground motion would influence the orbit stability.The ground motion of SSRF is severe.It is essential to control the vibration of the mechanical components.Vibration damping is an effective method to control the vibration.The author designed a vibration damping structure for the SSRF mechanical components.The test results show that it can effectively control the mechanical vibration.

新能源重卡特定车速驾驶室抖动问题研究

在路试时发现,某新能源重卡以特定车速行驶时,驾驶室出现低频抖动现象。通过对车辆道路试验进行振动加速度测试,结合偏频测试和频谱分析、相干分析,找出了该抖动的激励源及传递路径。分析结果表明:当车速在47 km/h左右时,车轮产生的动不平衡激励频率与后悬簧上偏频处在共振区间,放大了车轮旋转激励向车身的传递,导致此特定车速的异常抖动现象。针对此抖动分别从源头和传递路径上提出改进建议,消除了抖动现象,并为该类问题提供了一种有效的故障诊断方法和改进建议。

高速胶印机关键技术研究现状及进展

高速胶印机图文转移及印刷缺陷机理非常复杂。很多学者采用有限元方法分析了图文转移机理及起褶缺陷的成因。非线性振动测试实验研究表明,高速胶印机的非线性振动及印刷滚筒齿轮的传动误差导致了墨杠缺陷。通过印刷实验得到了材料的印刷适性及影响印刷品质量的因素。在对国内外研究现状分析的基础上,指出了胶印机有待解决的5个关键技术问题:非线性振动对印刷过程的影响、图文转移机理、印刷品质量在线检测、材料印刷适性、卷筒纸印刷机的张力控制。