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）.

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.

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.

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.

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.

A modeling analysis of molecular orientation at interfaces by polarization-dependent sum frequency generation vibrational spectroscopy

Sum frequency generation(SFG) vibrational spectroscopy has been proven an excellent tool to measure the molecular structures, symmetries and orientations at surfaces/interfaces because of its strong polarization dependence. However, a precise quantitative analysis of SFG spectral intensity and molecular orientation at interfaces must be carefully performed. In this work, we summarized the parameters and factors that are often ignored and illustrated them by evaluating studies of CO adsorption on the(111) facet of platinum(Pt) and palladium(Pd) single crystals at the gas(ultra-high vacuum, UHV)/solid interfaces and methanol(water) adsorption at the air/liquid(solid/liquid) interfaces in the presence of sodium iodide(chloride) salts. To intuitively estimate the influence of incidence angles and refractive indices on the SFG intensity, solely a defined factor of|Fyyz| was discussed, which can be individually separated from the macroscopic second-order non-linear susceptibility χ yyz^(2) term and represents the SSP intensity. Moreover, effects of refractive indices and the molecular hyperpolarizability ratio(R) were discussed in the orientational analysis of interfacial CO and methanol molecules. When IPPP/ISSP was identical, molecules with a larger R had smaller tilting angles(q) on Pt(assuming q < 51°), and CO molecules on Pd would tilt much closer to the surface than they did on Pt. A total internal reflection(TIR) geometry enhanced the SFG intensity, but it also amplified the influence of refractive index on SFG intensity at the solid(silica)/liquid interface. The refractive index and R-value had similar influence on the methanol orientation in the presence of sodium iodide salts at air/liquid and solid/liquid interfaces. This work should provide a guideline for analyzing the orientation of molecules with different R, which are adsorbed on catalysts or located at liquid interfaces involving changes of refractive indices.

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.

Optical Sum Frequency Generation Spectroscopy of Cracked Non-Glutinous Rice (Oryza sativa L.) Kernels

In order to study the correlation between the cracking of rice (Oryza sativa L.) kernels and the molecular structure of the amylopectin in them, we attempted optical sum frequency generation (SFG) spectroscopy in the C-H stretching vibration region for normal and cracked japonica non-glutinous rice kernels. The samples were Koshihikari and Nipponbare. In Nipponbare, the width of the SFG spectrum peak at 2915 cm- 1 of the cracked rice kernels was broader than that of the normal ones, while for Koshihikari there was no clear difference. The width of the 2915 cm- 1 peak is suggested to originate from the variety of the higher-order structure of the saccharide chains in amylopectin. Although this is a tentative result, this method is shown to have a potential of serving for preventing the cracking of the rice kernels.

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.

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.

Ordering effects of cholesterol on sphingomyelin monolayers investigated by high-resolution broadband sum-frequency generation vibrational spectroscopy

This report investigated the ordering of the alky chain of sphingomyelin （SMs） monolayers induced by cholesterol at the air/water interface using high-resolution broadband sum frequency generation vibrational spectroscopy （HR-BB-SFG-VS）. The SFG spectra of the three nature sphingomyelin/cholesterol mixture monolayers with two concentrations of the cholesterol at the air/water interface are performed under different polarization combination. A new resolved CH2 symmetric stretching （d＋, ~2834 cm-1） and the CH3 symmetric stretching （r＋, ~2874 cm-1） mode are applied to characterize the conformational order in the sphingomyelin/cholesterol mixture monolayers. It was found that the cholesterol make the sphingosine backbones more conformational order. During this process, the conformational order of the N-linked acyl chain remains unaltered. Moreover, the sphingosine backbones of SMs have much larger contributions to gauche defects of SMs than one in the N-linked acyl chain. These results presented here not only shed lights on understanding of the interactions of sphingomyelin molecules with cholesterol molecules at interface but also demonstrates the ability of HR-BB-SFG to probe such complicated molecular systems.

Surface of room temperature ionic liquid [bmim][PF_6] studied by polarization- and experimental configuration-dependent sum frequency generation vibrational spectroscopy

Understanding and control of the surface properties such as molecular orientations are of great importance in numerous applications of ionic liquids. However, there remain discrepancies among the previous experimental and theoretical studies on the surface orientation and structures of room temperature ionic liquids(RTIL) systems. In this article, the orientation of 1-butyl-3-methylimidazolium([bmin]) cation at the air/liquid interface of a characteristic RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate([bmim][PF6]), was investigated by the sum frequency generation vibrational spectroscopy(SFG-VS). Detailed polarization and experimental configuration analyses of the SFG-VS spectra showed the possibility of a small spectral splitting in the CH3 symmetric stretching region, which can be further attributed to the probable existence of multiple orientations for the interfacial [bmim] cations. In addition, the(N)–CH3 vibrations were absent, ruling out the prediction by several recent molecular dynamics simulations which state that portions of the [bmim] cations orient with a standing-up(N)–CH3 group at the ionic liquid surface. Hence, new realistic theoretical models have to be developed to reflect the complex nature of the ionic liquid surface.

Interfacial Water Structure in Langmuir Monolayer and Gibbs Layer Probed by Sum Frequency Generation Vibrational Spectroscopy

Langmuir monolayer and Gibbs layer exhibit surface-active properties and it can be used as simple model systems to investigate the physicochemical properties of biological membranes. In this report, we presented the OH stretching vibration of H2O in the 4＂-n-pentyl-4-cyano-p-terphenyl （5CT）, nonadecanenitrile （C18CN） Langmuir monolayer and compared them with CH3CN Gibbs layer at the air/water interface with polarization SFG-VS. This study demonstrated that the hydrogen bond network is different in the Langmuir monolayer of 5CT, C18CN from CH3CN Gibbs layer at the air/water interface which showed two different water structures on the different surface layer. The results provided a deeper insight into understanding the hydrogen bond on the interfaces.

甲烷水合物成核过程的实验研究进展(特邀)

甲烷水合物(可燃冰)作为一种储量巨大、分布广泛的清洁能源而备受关注。围绕甲烷水合物的开采、以固态水合物形式储运天然气和氢气等问题开展基础科学研究,具有重要的科学意义和应用价值。成核过程是甲烷水合物形成的关键第一步,由甲烷、水分子形成团簇并逐渐演化形成水合物的微观过程。然而,由于缺乏在高压环境下研究成核微观过程的有效实验方法,针对成核过程的实验研究进展缓慢。本文首先对气体水合物的结构及其性质进行了回顾;然后,以水合物演化的分子动力学模拟为基础,梳理现有关于水合物演化路径的初步认知;最后,以超快非线性光谱学方法为主,讨论了水合物实验研究的进展和展望。

和频与差频振动光谱实验构型的分析模拟

实验构型分析是定量分析和频振动光谱的基础.变换实验构型,不仅要考虑某一振动模式信号强度的大小,还要考虑不同构型下的信号检测效率.现有的和频振动光谱实验构型分析主要考虑前者.本文探讨实验构型分析中所涉及的信号检测效率问题,模拟在共向式和频(差频)及对射式和频(差频)振动光谱实验中选取何种实验构型对采集信号光更加合理有效.利用相干光学过程能量守恒和动量守恒原理,分析了入射角及入射光频率等因素对信号出射角的影响,并模拟了信号出射角与入射角及入射光频率的关系,得到了可选的入射角组合最多、出射角随入射光频率变化最小的实验构型.结果表明,和频振动光谱采取共向式实验构型,差频振动光谱采取对射式实验构型,有利于信号采集,进而有利于用实验构型分析方法对和频(差频)振动光谱进行定量研究.

和频光谱研究萃取剂TOPO分子在空气/水界面处的取向行为

采用和频光谱研究了萃取剂TOPO分子在空气/水界面处的取向行为。研究发现,在不同膜压条件下,TOPO分子在水表面排布的有序化程度不同。膜压越大,TOPO分子在水表面的堆积密度越大,其分子碳链的取向越倾向于垂直空气/水界面。研究萃取剂分子在界面的取向行为,可以为理解界面处萃取剂分子与目标待萃取离子的相互作用机理提供思路。

不同受限状态下链硫醇的非线性光学响应

以和频(SFG)振动光谱技术探测了正十二硫醇(DDT)在不同受限状态下的分子振动信号,包括金属基底上的自组装单层(SAM)分子,放置在二氧化硅基底上的表面DDT化的金纳米粒子以及金纳米粒子的甲苯溶液.在三种状态下都探测到了来自于DDT分子的振动光谱,振动光谱的区别提供了在不同受限态下DDT分子的结构信息.在金属基底上DDT分子排列规整,放置在二氧化硅基底上的金纳米粒子表面的DDT分子具有一定的柔性,在空气-甲苯溶液界面金纳米粒子表面的DDT分子高度无序.此外,光谱实验显示,金纳米粒子表面的分子振动信号产生了局域场增强的效应,相对于金基底上的自组装单层分子而言,增强系数为102-103,取决于光谱的偏振组合.

PEO-PPO聚醚嵌段共聚物的表面活性及其在溶液界面的结构

利用和频振动光谱及表面张力测定技术对两亲性聚氧乙烯-聚氧丙烯(PEO-PPO)表面活性剂的表面活性及溶液界面结构进行了研究。结果表明:疏水PPO链段在溶液界面吸附并紧密排列是溶液表面张力降低的主要原因。增加溶液浓度、增大共聚物链内PPO与PEO聚合度比值可增加高分子链在界面的吸附,并使PPO在界面紧密排列,侧基(甲基)有序取向。另外,PPO在分子链中的位置也对这一行为产生影响,PPO位于分子链两端时的结构更有利于PPO在表面紧密堆积,降低界面高分子链间相互作用,减小溶液表面张力。

和频振动光谱中基底信号对分子信号的影响

和频振动光谱中基底信号和分子共振信号发生相干叠加,因此在分析和频振动光谱时需要考虑基底信号的影响。使用和频振动光谱分析金表面的正十八烷基硫醇自组装分子膜,结果表明,基底信号不仅使分子信号从正峰变为负峰,还能够使弱的分子信号在和频振动光谱中得到增强。

有序分子系统的线性与非线性光谱学的简化描述(英文)

通过对有序分子系统的线性与非线性光谱学的简化描述 ,帮助对有序分子体系光谱学进行研究的实验学家建立明确的物理图像和定量的研究工具 .这一描述是从最近对二阶非线性光学界面研究技术 ,即光学二次谐波 (SHG)和和频偏振振动光谱 (SFG VPS)的定量取向和偏振处理中推广出来的 .这一处理的方法关键在于简化线性和非线性光学中的有效极化率 ,构造出一个通用的取向泛函 ,并能通过实验参数清晰地计算出取向泛函的取向和强度因子 .同时还讨论了相干光谱技术在准确测量有序分子体系的取向和序的相比于非相干光谱方法的优点 .