金属纳米椭球结构表面的局域电场和吸附分子分布

过渡金属纳米结构表面吸附CO分子时会出现异常红外效应,这一现象可以用纳米结构表面吸附分子在外电场作用下产生局部凝聚从而相互作用能增加来解释.在前期研究的基础上,给出金属基底表面生长出的纳米颗粒为椭球状颗粒的理论计算结果.基于均匀外电场中金属纳米椭球颗粒按一定对称性排列的表面结构模型,用经典电磁学理论计算了纳米椭球颗粒表面附近的局域电场.在此基础上,将吸附的CO分子等效为偶极子,在考虑了偶极子与局域电场、偶极子之间以及偶极子与金属基底三种相互作用的情况下,用Monte-Carlo方法进行数值模拟,最后给出纳 关键词： 金属纳米结构表面 纳米椭球 吸附分子 局域电场     

金属纳米结构表面吸附的CO分子在外电场中的相互作用

建立金属纳米颗粒在外电场中的排列结构模型，用经典理论分析纳米结构金属表面上吸附的CO分子在外电场中的相互作用能，包括有效偶极子间的相互作用和与局域电场的相互作用，并讨论和计算了纳米颗粒表面附近的局域电场. 用Monte-Carlo方法进行数值计算和模拟，具体给出纳米颗粒表面CO分子的分布和相互作用能，表明金属表面纳米结构使CO产生凝聚，并使分子相互作用能增加，为解释异常红外吸收效应提供依据. 关键词： 纳米结构金属 吸附分子 相互作用 局域电场     

Cu(100)表面CO分子单层膜的原子结构

利用第一性原理研究了覆盖度分别为1.00, 0.50和0.25 ML时CO分子单层膜在Cu(100)表面的吸附系统. 计算表明CO分子对不稳定. 获得了CO分子单层膜在虚拟Cu(100)表面的原子结构, 以及CO分子单层膜在Cu(100)表面吸附系统的原子结构. 当CO分子单层膜在Cu(100)表面的三个吸附位吸附, 覆盖度为1.00 ML时, 顶位和桥位都稳定, 而空心位不稳定; 覆盖度为0.50和0.25 ML时, 三个吸附位都稳定.比较吸附前后CO分子单层膜的原子结构, 可知CO分子和Cu(100)表面的相互作用强于CO分子单层膜之间的相互作用. 关键词： CO分子单层膜 自组装 CASTEP Cu(100)     

激光拉曼光谱研究苏丹红Ⅲ分子的吸附方式

用近红外傅里叶拉曼光谱研究了苏丹红Ⅲ分子在覆银纳米颗粒的抛光铝片表面上的吸附行为,得到了一系列高质量的增强拉曼散射（SERS）谱图。对苏丹红Ⅲ分子在银胶溶液、覆银滤纸、覆银粗糙铝片上的SERS谱进行比较,结果表明苏丹红Ⅲ分子在各基底上与银纳米颗粒表现出不同的吸附行为。在银胶溶液中,苏丹红Ⅲ分子主要是通过N=N双键吸附在银纳米颗粒上的;在沉积了银纳米颗粒的滤纸表面,同样地,主要是由N=N双键吸附;而在沉积了银纳米颗粒的抛光铝片表面,不仅N=N双键参与了吸附,苏丹红Ⅲ分子中的羟基与银颗粒有相互作用,并且铝片上的氧化铝颗粒也可能吸附了苏丹红Ⅲ分子。     

纳米结构Pt膜上CO吸附的异常红外效应机理研究

CO吸附在经方波电势处理后的纳米结构Pt金属膜电极上可观察到异常红外效应（AIREs）.在实验基础上用粒子间的相互作用和电子-空穴衰减机理分析、模拟了AIREs，表明Pt金属表面的纳米岛状结构增强了CO分子间及CO分子与纳米结构表面的相互作用，电子-空穴衰减引起的能量转移和粒子间相互作用的增强可以导致异常红外吸收谱线变化特征的出现. 关键词： 异常红外效应 粒子相互作用 电子-空穴衰减     

带电纳米颗粒与相分离的带电生物膜之间相互作用的分子模拟

纳米颗粒在纳米医药、细胞成像等领域有着非常广泛的应用,深入理解纳米颗粒与生物膜之间相互作用的微观机制是纳米颗粒合成与应用的重要基础.本文采用粗粒化分子动力学模拟的方法研究了带电配体包裹的金纳米颗粒与相分离的带电生物膜之间的相互作用.结果表明,通过改变金纳米颗粒表面的配体密度、配体带电种类和比例,以及膜内带电脂分子的种类,可以方便地调控纳米颗粒在膜表面或膜内停留的位置和状态.进一步从自由能的角度分析了带电纳米颗粒与带电生物膜之间相互作用的微观物理机制.本文对纳米粒子在纳米医药、细胞成像等领域的应用具有一定的理论参考意义.     

二维自组装结构中银纳米粒子的吸收光谱特征

通过静电相互作用在聚乙烯吡啶修饰的玻璃表面组装了银纳米粒子的二维结构。吸收光谱结果表明,组装银粒子间的相互作用导致银粒子的偶极子表面等离子体共振发生较大的位移,但基本不改变四极子表面等离子体共振。银粒子表面吸附分子及周围介质直接影响其表面等离子体共振。     

重力对金纳米颗粒在生物膜表面吸附影响的荧光研究

纳米颗粒在生物膜表面的吸附行为是纳米生物技术领域的重要问题. 采用正、倒置实验, 通过荧光显微镜定量研究了重力对金纳米颗粒在支撑磷脂膜表面吸附的影响. 研究发现, 颗粒尺寸决定其在顶或底层支撑膜表面吸附的差异性. 吸附量的差异与颗粒的沉淀速率和扩散速率之比的对数呈线性关系. 粒径小于14 nm时, 不考虑重力在吸附时的影响; 粒径大于176 nm时, 重力在吸附中占主导地位. 为药物载体研究和理解颗粒－生物膜相互作用提供参考.     

重力对金纳米颗粒在生物膜表面吸附影响的荧光研究

纳米颗粒在生物膜表面的吸附行为是纳米生物技术领域的重要问题.采用正、倒置实验,通过荧光显微镜定量研究了重力对金纳米颗粒在支撑磷脂膜表面吸附的影响.研究发现,颗粒尺寸决定其在顶或底层支撑膜表面吸附的差异性.吸附量的差异与颗粒的沉淀速率和扩散速率之比的对数呈线性关系.粒径小于14 nm时,不考虑重力在吸附时的影响;粒径大于176 nm时,重力在吸附中占主导地位.为药物载体研究和理解颗粒-生物膜相互作用提供参考.     

过渡区内纳米颗粒的曳力特性模拟研究

在过渡区内,关于纳米颗粒曳力计算及输运特性的研究较为困难,通常会采用一些近似方法,将自由分子区或者连续介质区的理论计算式进行修正,以适用于过渡区,但是其准确性值得商榷.本文基于分子动力学模拟方法,研究了过渡区内纳米颗粒的曳力特性,并与相关理论进行对比.结果表明,气-固分子间相互作用对纳米颗粒的曳力具有显著影响.当气固结合强度较弱时,理论计算结果与分子动力学模拟值吻合较好;当气固结合强度较强时,分子动力学模拟结果明显大于理论值,这是由于气体分子在纳米颗粒表面的吸附所导致.基于气体分子在颗粒表面的吸附特性,提出引入有效颗粒半径修正,其过渡区内曳力的理论计算结果与分子动力学模拟结果吻合较好.     

Local electric field and configuration of CO molecules adsorbed on a nanostructured surface with nanocones

Based on the nanostructured surface model that the (platinum, Pt) nanocones grow out symmetrically from a plane substrate, the local electric field near the conical nanoparticle surface is computed and discussed. On the basis of these results, the adsorbed CO molecules are modelled as dipoles, and three kinds of interactions, i.e. interactions between dipoles and local electric field, between dipoles and dipoles, as well as between dipoles and nanostructured substrate, are taken into account. The spatial configuration of CO molecules adsorbed on the nanocone surface is then given by Monte-Carlo simulation. Our results show that the CO molecules adsorbed on the nanocone surface cause local agglomeration under the action of an external electric field, and this agglomeration becomes more compact with decreasing conical angle, which results in a stronger interaction among molecules. These results serve as a basis for explaining abnormal phenomena such as the abnormal infrared effect (AIRE), which was found when CO molecules were adsorbed on the nanostructured transition-metal surface.     

Excitation of adsorbed molecule vibrations in low energy electron scattering

We develop a theory of low energy electron loss spectroscopy of vibrational modes of molecules adsorbed on metal surfaces. Differential and total cross sections are calculated in the Distorted Wave Born Approximation, assuming i) strong elastic scattering on the metal surface, ii) direct electron-molecule interaction via the electric dipole field associated with the molecular vibration. The angular distributions are calculated and discussed for molecules adsorbed at various distances above the metal surface and for several electron energies and impact angles. The influence of electronic screening of dipolar oscillations is discussed and the consequences of the classical induced image dipoles are explored. It is shown that the metal surface selection rule known in IR spectroscopy is only approximately valid in electron scattering. Finally, we give numerical estimates of the inelastic scattering cross sections for the stretching vibrations of CO molecule adsorbed on transition metal surfaces, in reasonable agreement with experiments.     

Field enhancement at crystal steps: An intensity effect in vibrational spectra of adsorbed molecules

An enhancement of the electric field near a step in a single-crystal metal surface could give rise to an increase in the molar extinction coefficient for molecules adsorbed on the step. For CO adsorbed on a stepped surface. Pt(S)-[4(111)×(100)]. we calculate the extinction coefficient to be about 2.2 times greater for molecules adsorbed on the step than for molecules adsorbed on the middle of the terrace.     

Local field distribution and configuration of CO molecules adsorbed on the nanostructure platinum surface

This paper shows that the local electric field distribution near the nanostructure metallic surface is obtained by solving the Laplace equation, and furthermore, the configuration of CO molecules adsorbed on a Pt nanoparticle surface is obtained by using Monte Carlo simulation. It is found that the uneven local electric field distribution induced by the nanostructure surface can influence the configuration of carbon monoxide (CO) molecules by a force, which drags the adsorbates to the poles of the nanoparticles. This result, together with our results obtained before, may explain the experimental results that the nanostructure metallic surface can lead to abnormal phenomena such as anti-absorption infrared effects.     

Electrostatic Nature of Size Dependences of Adsorption Properties of Ytterbium Nanofilms Grown on the Surface of Silicon: the CO–Yb–Si(111) System

The adsorption of CO molecules onto ytterbium nanofilms with their thickness varying from 1 to 16 monolayers is studied. The dependences of the number of adsorbed CO molecules (adsorption isotherms) and the work function of ytterbium films on the dose of carbon monoxide are examined. It is demonstrated that both the number of adsorbed molecules and the work function depend (under equal conditions) on the nanofilm thickness; in other words, a size effect is revealed. It is found that this size effect is induced by the electrostatic interaction between the conduction electrons of ytterbium and the electrons localized on the nanofilm surface, which establish bonding between the surface and CO molecules. This interaction depends on the film thickness and limits the number of CO molecules that may be adsorbed onto the surface of a film with a given thickness.

     

Frequency shifts in the spectra of molecules adsorbed on metals,with emphasis on the infrared spectrum of adsorbed CO

Two processes are considered which cause the frequency of the band maximum in the infrared absorption spectrum of molecules adsorbed on metals to shift with increasing coverage. The first arises from the coverage-dependent modification of the local field acting on an adsorbed molecule while the second originates from vibrational coupling arising from a through-metal interaction between molecules adsorbed on different metal atoms. Infrared absorption strengths are discussed and the method used heretofore to obtain the extinction coefficients of adsorbed molecules is questioned. In particular, a factor of 2 which results from the constructive superposition of the incident and reflected electric fields is shown to be often ignored. We show that dipolar (through-space) coupling is too weak to account for the magnitudes of the shifts recently observed for CO on single-crystal Pt and Pd as coverage progressed from low to high values. Vibrational coupling is also shown to account for the disparity in the intensities of the two bands observed when ¹²CO and ¹³CO are coadsorbed on supported metals. Similar experiments on single-crystal surfaces are suggested to help determine to what extent the observed spectral frequency shifts are derived from adsorbate—adsorbate coupling as opposed to other mechanisms.     

Oxygen KLL Auger spectra from O2 and CO adsorbed on Ni

High resolution oxygen KLL Auger spectra from O₂ and CO adsorbed on clean Ni (110) have been measured and compared. These Auger spectra are quite different from one another and are compared with spectra of the free molecules. Similarities between the oxygen spectra from adsorbed and gaseous CO are noted and interpreted as due to the weak bonding of CO to Ni with the O atom furthest from the surface. These Auger studies also characterize the change in bonding of adsorbed CO due to electron beam interaction.     

Electric potential distribution near nanocone arrays on metal substrates

Based on the nanostructured surface model,where conical nanoparticle arrays grow out symmetrically from a plane metal substrate,a theoretical model of the local electric potential near nanocones is built when a uniform external electric field is applied.In terms of this model,the electric potential distribution near the nanocone arrays is obtained and given by a curved surface using a numerical computation method.The computational results show that the electric potential distribution near the nanocone arrays exhibit an obvious geometrical symmetry.These results could serve as a basis for explaining many abnormal phenomena,such as the abnormal infrared effects(AIREs) which are found on nanostructured metal surfaces,as well as a reference for investigating the applications of nanomaterials,such as nanoelectrodes and nanosensors.