Vibrational Spectroscopy of Surface Adsorbates by Sum Frequency Generation (SFG)

The vibrational spectroscopy by way of vibrational sum-frequency generation (VSFG) has been made of formic acid adsorbed on MgO(001) surface and of n-alkyltrichlorosilanes chemisorbed on quartz plates. It was revealed that the species on the MgO surface was formate ion (HCOO⁺) with CH bonds standing vertical to the surface and that the different adsorption sites showed up on repeated cycles of adsorption-desorption processes. The results of chemisorbed films indicated that the g-t and/or g-t-g′ conformational scquences of n-alkyl chains occurred more frequently by the length of alkyl chain and that the surface hydroxyls, which are the sites of chemisorption, are ripped off by pre-exposure of substrate to oxygen plasma.     

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(SFG-VS)研究超铺展三甲基硅烷表面活性剂在空气/水界面的振动光谱和吸附

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 cm-1 (mostly the asymmetric stretch or AS mode), and with the weak but apparent contribution from the -O-CH2- groups around 2880 cm-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±0.8kJ/mol, indicating the unusually strong adsorption ability of the Silwet L-77 superspreading surfactant     

Molecular origins of the remarkable chiral sensitivity of second-order nonlinear optics.

Recent observations of remarkably large chiroptical effects in second-harmonic generation (SHG) and sum-frequency generation (SFG) measurements suggest exciting possibilities for the development of new chiral-specific spectroscopies and novel chiral materials for nonlinear optics. Several fundamental studies designed to elucidate the molecular and macromolecular origins of the chiral responses are reviewed to provide a framework for development of this emerging field. In general, the chiral activity in SHG and SFG has the potential to arise from complex interactions between hosts of different competing effects. Fortunately, relatively simple electric dipole-allowed mechanisms routinely dominate the nonlinear optical chiral activities of most practical systemsexpressions can often be generated to link the. This substantial reduction in complexity allows for the development of simple models connecting the macroscopic nonlinear optical response to intuitive molecular and supramolecular properties.     

Tunable UV generation at 283 nm by frequency doubling and sum frequency mixing of two semiconductor lasers for the detection of Pb

High resolution atomic absorption measurements of lead at 283 nm in a vapor cell were performed by frequency doubling an 850 nm laser diode to obtain 425 nm light, followed by sum frequency generation of the harmonic radiation with a second 850 nm laser diode.     

氟化单元封端的不同聚合度PBMA甲苯溶液气/液界面结构

采用ATRP技术合成具有不同聚合度的末端连接甲基丙烯酸全氟辛基乙酯(FMA)单元的聚甲基丙烯酸丁酯(PBMAm-ec-PFMAn).利用和频振动光谱(SFG)和表面张力测定技术研究了各种氟化聚合物溶液的气/液界面结构.发现PBMAm-ec-PFMAn甲苯溶液的表面活性及其气/液界面的结构与两种结构单元数密切相关.当PFMA聚合度(n)大约为4和6时,聚合物溶液的表面张力随着PBMA聚合度的增加从21增加到25mN/m(该值与PBMA均聚物溶液相同).SFG的研究结果表明PBMA段较长时溶液表面被PBMA所占据.PBMA段较短时,PFMA组分吸附在溶液表面,排列比较有序且紧密堆积.当PBMA末端只有1个FMA单元时,其甲苯溶液的表面张力随PBMA段长稍有增加(从22增加到23mN/m),其值介于21与25mN/m之间.研究表明当PBMA段较短时,可能聚合物中的氟化组分吸附在溶液表面,但其排列的有序性较差.随着PBMA聚合度的增加,氟化组分与PBMA组分可能同时占据在溶液表面,这时其表面张力大约为23mN/m.     

氨基酸分子的光学活性和频效应

用带限制场Hartree-Fock (RHF/6-311++G^**)从头算的方法进行分子构型优化, 单激发态组态相互作用(CIS/6-311++G^**)计算各种需要的相关数据; 应用态求和理论, 以长度偶极矩和速度偶极矩两种形式模拟了一系列氨基酸离子的光学活性和频效应(OA-SFG)光谱. 结果表明速度偶极矩计算得到的一系列氨基酸离子的和频效应光谱强度顺序能很好地与实验相吻合, 而长度偶极矩形式计算得到的结果与实验不吻合. 引起这两种形式和频效应光谱理论计算结果差别的原因是由于长度偶极矩形式具有原点敏感性, 而速度偶极矩没有. 速度偶极矩方法更适用于分子光学活性和频效应的模拟.     

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.     

Aqueous Heterogeneity at the Air/Water Interface Revealed by 2D‐HD‐SFG Spectroscopy

Water molecules interact strongly with each other through hydrogen bonds. This efficient intermolecular coupling causes strong delocalization of molecular vibrations in bulk water. We study intermolecular coupling at the air/water interface and find intermolecular coupling 1) to be significantly reduced and 2) to vary strongly for different water molecules at the interface—whereas in bulk water the coupling is homogeneous. For strongly hydrogen‐bonded OH groups, coupling is roughly half of that of bulk water, due to the lower density in the near‐surface region. For weakly hydrogen‐bonded OH groups that absorb around 3500 cm^?1, which are assigned to the outermost, yet hydrogen‐bonded OH groups pointing towards the liquid, coupling is further reduced by an additional factor of 2. Remarkably, despite the reduced structural constraints imposed by the interfacial hydrogen‐bond environment, the structural relaxation is slow and the intermolecular coupling of these water molecules is weak.