对巯基吡啶在纳米银上的SERS化学增强机理

以对巯基吡啶分子吸附在纳米银上的SERS光谱为研究对象,通过密度泛函理论计算和拉曼散射理论分析,详细地探讨了该分子的吸附结构、异构化、氢键作用和低能激发电荷转移态的性质,模拟了当该分子以不同结构吸附在银上的SERS光谱,研究了其吸附结构与SERS光谱之间的对应关系。理论结果也表明,在SERS增强机理研究中,分子与金属纳米结构和环境的作用是影响SERS光谱的主要影响因素。当激发光的能量与低能激发电荷转移态的能量匹配时,显著影响SERS光谱强度。     

过渡金属表面紫外线激发的表面增强Raman光谱(UV-SERS)研究

本文以紫外光325 nm作为激发线,成功获得了不同形貌的铂纳米粒子(铂纳米立方体和纳米絮状物),电化学粗糙的钴和镍电极在紫外区的表面增强拉曼散射(UV-SERS)效应。同时发现不同形貌的铂纳米结构在紫外区有不同的SERS效应,不同金属在紫外区的增强效应也不同,其中铂纳米立方体产生了最好的增强效应,这一结果也预示有必要发展更优的基底。为了利用UV-SERS研究具有重要应用意义的分子,同时也为了验证铂纳米立方体在紫外区的增强效应具有分子的普适性,我们研究了CO和腺嘌呤分子吸附在铂纳米立方体上的UV-SERS。     

不同结构Cu_2S-Ag复合基底的SERS光谱研究

随着SERS技术的迅猛发展以及科研人员的不断探索,我们已经发现了很多半导体材料都具有较好的SERS活性。为了进一步探讨金属-半导体体系的电荷转移过程并扩展半导体材料在SERS领域的应用,本研究小组制备了具有不同结构的贵金属Ag-半导体Cu_2S复合基底,并在吸附探针分子后对基底的SERS表现进行了分析。这种方法通过控制基底中不同成分的组成,实现对SPR的调控,该方法不仅显著提高了被检测探针分子的信号强度,还克服了长久以来基底对于激发光波长依赖的特性,可以实现多种激发波长下的拉曼增强,有望广泛应用于拉曼分析检测中。     

三维时域有限差分法计算金纳米粒子尺寸与SERS活性的关联

通过合成一系列不同粒径(16～160 nm)的金纳米粒子.观察到120～135 nm的金纳米粒子在632.8nm波长激发下具有最高的SERS活性,这与前人报道的电磁场理论及实验的结果不同.利用三维时域有限差分法对金纳米粒子的SERS活性与其尺寸以及入射光波长的关系进行模拟计算.在632.8 nm激发线下,金纳米粒子二聚体体系在粒径为110 nm左右具有最佳增强效应,其光电场耦合最强的热点处的增强因子高达109考虑到体系的平均SERS增强因子通常会比最大值低约2个数量级,计算得到的107的增强因子与实验测量值相符.同时对目前实验上尚难以合成的大尺寸的金纳米粒子进行模拟,结果表明受多极矩和大尺寸效应的影响在粒径220 nm时又出现SERS增强另一峰值.在325 nm的紫外激发线下,计算得到的增强因子仅为102.     

四苯基卟啉及其金属配合物在溴化银胶体上的表面增强喇曼光谱研究

研究了四苯基卟啉（H2TPP）及其金属配合物（AgTPP和MgTPP）在AgBr胶体上的表面增强喇曼光谱（SERS）。SERS光谱表明,吸附在ArBr胶体粒子表面的MgTPP和H2TPP分子分别发生银离子交换和银配位反应生成AgTPP,这种表面反应可能与激光照射有关。AgTPP分子在胶体粒表面的吸附导致卟啉大环的非平面化,使v8振动（M－N键伸缩振动）向高波数方向移动近10cm^-1。632.8nm激发下的表面喇曼谱以化学增强为主,而488.0nm激发下表面喇曼谱除化学增强效应外,还存在共振增强效应。     

P-thiocresol 吸附在银纳米粒子表面系统的表面增强拉曼散射和表面增强共振拉曼散射的增强研究

文中从实验和计算两方面报道了在514.5 nm激发光下P-Thiocresol吸附在银胶表面系统的表面增强拉曼散射(SERS).文中分析了它的增强机制,发现增强主要来自于电磁场增强.如果考虑距离为2nm的两个银纳米粒子的耦舍效应,两粒子之间的SERS的电磁场增强为7.16 × 107.静态化学增强亦起到部分增强作用,它的增强倍数为6.所以,总的SERS增强,包括静态化学增强和电磁场增强,是Gtotal=Gsc ×GEM=4.4×108.我们也理论地研究了此系统的表面增强共振拉曼散射(SERRS).当激发光与P-Thiocresol-Ag3系统的激发态共振时,电荷转移机制(化学增强)也将起到重要作用,最强的增强可迭106.我们使用电荷密度将激发光下p-Thlocresol和Ag团簇问的电荷转移结果可视化,这是电荷转移的直接理论证据.对于SERRS增强,包括电荷转移和电磁场增强机制,能达到1013.     

(Au-Probe)@SiO_2单层纳米粒子膜制备及表面增强拉曼光谱研究

表面增强拉曼光谱(SERS)因其高达单分子检测的表面灵敏度而广受青睐,其增强机理主要包括电磁场增强效应(EM)和电荷转移增强(CT)。通常,前者占主导作用,且局域电磁场可极大地增强表面吸附分子的拉曼信号。而介质通常对局域电磁场和EM增强有一定影响,从而影响SERS检测,通过壳层隔绝纳米粒子(SHINs)可避免介质与SERS增强源间的直接接触。但迄今为止,几乎未见有关介质对其增强拉曼光谱(SHINERS)影响的研究,主要因SERS基底均匀性较差所致。制备了两种探针分子内嵌且Au核尺寸不同的核壳纳米粒子,即(55 nm Au-PNTP)@SiO_2和(110 nm Au-pMBA)@SiO_2,壳层厚度分别为3.5和4.0 nm,壳层结构连续且无针孔效应。采用液-液两相成膜法制备其单层膜,转移至固相基底上可作为SERS基底,(55 nm Au-PNTP)@SiO_2单层膜上SERS谱峰强度的相对标准偏差约为5.38%,(110 nm Au-pMBA)@SiO_2单层膜上相对标准偏差约为5.97%,其重现性及均匀性优良,符合作为SERS基底的要求。研究它们分别在空气和水两种介质中的SERS效应,结果表明Au核被致密无针孔效应的SiO_2壳层包裹,且探针分子内嵌其中,由此完全隔绝了电磁场增强源内核Au纳米粒子与介质的直接接触,当改变基底所处的环境时,其实际介质仍为SiO_2,因此在两种介质中SERS信号几乎不发生改变。内嵌探针分子的PNTP或pMBA被包裹在SiO_2壳层内,溶剂及氧气等均无法参与反应,因此探针分子未发生SPR催化反应,保持稳定的光谱特征。由此可见内嵌探针分子的SERS信号强度及光谱特征不受介质的影响,可望作为多介质环境使用的高灵敏度SERS检测以及稳定内标或标记的重要基底。     

腺嘌呤的表面增强喇曼散射研究

本文是利用表面增强喇曼光谱研究腺嘌呤在银表面的吸附情况。为了避免外加阴离子产生的共吸附对SERS谱的影响,我们采用化学粗糙法(COR)进行银电极的表面处理。测量了不同电位时腺嘌呤的SERS谱,发现电位从正向负变化时腺嘌呤会以竖立武吸附变成接近平躺吸附。     

电化学体系中吸附在金电极表面吡啶的紫外拉曼光谱研究

观察到波长为325nm的紫外光激发下吸附在金电极表面的吡啶的表面增强拉曼光谱(SERS)。结合其SERS谱随电位的变化关系,分析了其中的增强机制并表明随电位的负移吡啶的吸附方式发生改变。     

4,4′-联吡啶吸附在银电极上的SERS谱的研究

本文根据0.005mol/L 4,4′-联吡啶/0.010mol/L氯化钾体系的循环伏安曲线、SERS光谱及随外加电位的变化情况,研究4,4′-联吡啶吸附在银电极上的SERS光谱及随外加电位的变化,探讨它们在银电极表面的吸附方式。一、引言自从发现吡啶吸附在银电极表面上产生表面增强喇曼散射(SERS)效应后,这个领域的研究日益深入。1987年,张     

Fluorescence as a Probe of Energy Dependence of Electron–Molecule Interaction

The fluorescence intensity dependences on electron kinetic energy, or fluorescence excitation functions, for some aromatic (perylene and p-terphenyl) and heterocyclic (biphenylfuran, oxazoles, and oxadiazoles) compounds are studied. It is found that the addition of phenyl rings to the above molecules result in a moderate decrease in excitation function. On the other hand, introducing heteroatoms such as oxygen or nitrogen leads to a substantial decrease in excitation function.     

The stereodynamic properties of the F+HO(v,j) → HF+O reaction on~1 A' and ~3A' potential energy surfaces by quasi-classical trajectory calculations:Initial excitation effect(v=1-3, j=0 and v= 0, j=1-3)

The stereodynamic properties of the F ＋ HO （v, j） reaction are explored by quasi-classical trajectory （QCT） calculations performed on the 1At and 3At potential energy surfaces （PESs）. Based on the polarization-dependent differential cross sections （PDDCSs） and the angular distributions of the product angular momentum with the reactant at different values of initial v or j, the results show that the product scattering and product polarization have strong links with initial vibrationalrotational numbers of v and j. The significant manifestation of the normal DCSs is that the forward scattering gradually becomes predominant with the initial vibrational excitation increasing, and the scattering angle of the HF product taking place on the 3At potential energy surface is found to be more sensitive to the initial value of v. The product orientation and alignment are strongly dependent on the initial rovibrational excitation effect. With enhancement in the initial rovibrational excitation effect, there is an overall decrease in the product orientation as well as in the product alignment either perpendicular to the reagent relative velocity vector k or along the direction of the y axis, for which the initial rotational excitation effect is much more noticeable than the vibrational excitation effect. Moreover, the initial rovibrational excitation effect on the product polarization is more pronounced for the 3At potential energy surface than for the 1At potential energy surface.     

Rectification of space-charge waves upon optical and electrical excitation

A comparative analysis is performed for three optical and electrical methods of exciting space-charge waves in photosemiconductors: (i) excitation by an external ac electric field combined with a static interference pattern, (ii) excitation by a moving interference grating, and (iii) excitation by an oscillating interference grating. It is shown that, in the case when space-charge waves are excited using a combination of all three methods, the dependence of the direct current passing through a sample on the excitation frequency exhibits two peaks that correspond to the resonant excitation of two modes of space-charge oscillations, namely, drift waves and trap recharging waves. It is noted that experimental observation of the peak attributed to the excitation of trap recharging waves should not pose any problems, whereas observation of the second peak associated with the excitation of drift waves is significantly complicated because of the small magnitude of the effect, especially for materials with a low electrical conductivity (or a long Maxwell relaxation time).     

Enhancing the photoluminescence intensity of silicon-rich nitride film by localized surface plasmon enhanced photo-excitation

The photoluminescence of silicon-rich nitride (SRN) film was coupled with the surface plasmon (SP) of Ag island film. It shows that the photoluminescence (PL) enhancement or quenching is strongly dependent on the excitation wavelength. When the excitation wavelength is near the SP resonance spectral region, the Ag islands act as a photo antenna, leading to the enhancement of the excitation cross-sections and therefore the photoemission enhancement. Furthermore, it is demonstrated that the metal island size also has an influence on the emission enhancement, but the enhancement is much more decided by the excitation wavelength than by the Ag island radiative scattering.     

New features in the anti‐Stokes and Stokes Raman spectra of single‐walled carbon nanotubes that are highly separated into their semiconducting and metallic nanotube components

Surface‐enhanced Raman scattering studies were performed using nonresonant (514.5 nm) and resonant (676.4 nm) optical excitations on single‐walled carbon nanotubes thoroughly separated into semiconducting (pure 99%) and metallic (pure 98%) components. Regardless of the support (Au or Ag), the metallic nanotubes do not present an anomalous anti‐Stokes Raman emission. Regardless of whether an on‐resonant or off‐resonant optical excitation is used, only the semiconducting nanotubes produce an abnormal anti‐Stokes Raman emission that grows when increasing the excitation light intensity or temperature. The Raman studies under light polarized relative to the main nanotube axis demonstrate that only semiconducting nanotubes are sensitive toward changes in the polarization of the excitation light. Copyright © 2014 John Wiley & Sons, Ltd.     

The stereodynamic properties of the F + HO (v,j)→HF + O reaction on the 1A' and 3A' potential energy surfaces by quasi-classical trajectory: Initial excitation effect (v =1-3, j = 0 and v = 0, j =1-3)

The stereodynamic properties of the F + HO (v, j) reaction are explored by quasi-classical trajectory (QCT) calculations performed on the ¹A' and ³A' potential energy surfaces (PESs). Based on the polarization-dependent differential cross sections (PDDCSs) and the angular distributions of the product angular momentum with the reactant at different values of initial v or j, the results show that the product scattering and product polarization have strong links with initial vibrational-rotational numbers of v and j. The significant manifestation of the normal DCSs is that the forward scattering gradually becomes predominant with the initial vibrational excitation increasing, and the scattering angle of the HF product taking place on the ³A' potential energy surface is found to be more sensitive to the initial value of v. The product orientation and alignment are strongly dependent on the initial rovibrational excitation effect. With enhancement in the initial rovibrational excitation effect, there is an overall decrease in the product orientation as well as in the product alignment either perpendicular to the reagent relative velocity vector k or along the direction of the y axis, for which the initial rotational excitation effect is much more noticeable than the vibrational excitation effect. Moreover, the initial rovibrational excitation effect on the product polarization is more pronounced for the ³A' potential energy surface than for the ¹A' potential energy surface.     

The influence of spread of excitation on the detection of amplitude modulation imposed on sinusoidal carriers at high levels

The improvement in amplitude modulation (AM) detection thresholds with increasing level of a sinusoidal carrier has been attributed to listening on the high-frequency side of the excitation pattern, where the growth of excitation is more linear, or to an increase in the number of "channels" via spread of excitation. In the present study, AM detection thresholds were measured using a 1000-Hz sinusoidal carrier. Thresholds for modulation frequencies of 4-64 Hz improved by about 10-20 dB as the carrier level increased from 10 dB SL (14.5 dB SPL on average) to 80 dB SPL. To minimize the use of spread of excitation with an 80-dB carrier, tonal "restrictors" with frequencies of 501, 801, 1210, and 1510 Hz were used alone and in combination. High-frequency restrictors elevated AM detection thresholds, whereas low-frequency restrictors did not, indicating that excitation on the high side is more important for detecting AM. Results of modeling suggest that the improvement in AM detection thresholds at high levels is likely due to the use of a relatively linear growth of response on the high-frequency side of the excitation pattern.     

Chatter suppression by parametric excitation: Model and experiments

Chatter vibration leads to challenges in precise machining due to its harmful effect on productivity and surface quality. In this study, a chatter suppression method based on parametric excitation was developed. The effect of parametric excitation on self-excited vibration was investigated based on a model of a van der Pol-Mathieu-Duffing oscillator with a time delay. It reveals that there can be a zero solution for the oscillator under the effect of parametric excitation, while it is impossible to have a stable zero equation without parametric excitation. The stability of a parametrically excited vibration system regarding the regenerative effect in the cutting processes was studied by the averaging method. The stability analysis shows that parametric excitation with an appropriate frequency and large amplitude has a chatter suppression effect no matter whether the waveform is a sinusoidal wave, square wave or triangular wave. To validate the effect of parametric excitation for chatter suppression, experiments were conducted based on a magnetorheological (MR) fluid-controlled boring bar, which can generate high-frequency parametric excitation based on the quick response of the MR fluid. Cutting experiments with an excitation current of different waveforms and diverse frequencies show that chatter can be significantly suppressed by the effect of parametric excitation.     

Controlled excitation of resonance self-oscillations in one-dimensional distributed systems

On the basis of the method of equivalent linearization combined with the method of moments, laws of self-oscillation excitation are obtained that provide the modes with maximum intensity of resonance (or quasi-resonance) oscillations in one-dimensional systems with distributed parameters. A restriction of a general type is imposed on the law of excitation. In the particular case of an integral quadratic restriction, the law of excitation leads to the generation of purely harmonic self-oscillations. The use of an extended (multiplicatively stabilizing) control provides the uniqueness and stability of the quasi-optimal mode of self-oscillation.