并五苯分子在Ag(110)表面成膜过程中的结构研究

采用低能电子衍射原位研究了并五苯分子（C₂₂H₁₄）在Ag(110)单晶表面的生长，观察了在初期沉积过程及随后基底变温过程中分子层结构的形成和变化.室温下并五苯分子在Ag(110)基底表面具有高的迁移性，从开始无序的亚单层膜结构逐渐形成有序的单层膜结构．实验和理论分析表明：并五苯分子平铺在Ag(110)表面，形成了与基底构成有关的有序结构，存在沿基底晶向成镜面对称的两种畴界取向，在基底温度从室温升高到接近并五苯升华温度的过程中，基底上的有序分子层结构保持稳定不变 关键词： 并五苯 低能电子衍射图案 分子层结构 Ag(110)     

扫描隧道显微镜功能化针尖对分子能级的选择成像

文章提出了一种通过修饰STM针尖使其功能化，调节扫描隧道显微镜（STM）的扫描偏压范围，实现对分子能级的选择性成像的方法．二萘嵌苯分子在Ag（110）表面上自组织形成的有序单层膜主要是通过分子的π电子态成像，而被二萘嵌苯分子修饰的STM针尖的能级失配于基底上吸附的分子的能级，从而只对分子的部分能级成像．这个结果为有机界面电子输运测量提供了一种更好的能级选择方法．     

十二烷基苯磺酸在掺杂态聚苯胺LB膜中的分子取向

本文利用偏振红外光谱,研究了十二烷基苯磺酸分子在掺杂态聚苯胺ＬＢ膜中的分子取向。计算结果表明,十二烷基苯磺酸分子的烷基链是与基底法线方向呈１７°角度排布的,由Ｘ射线小角衍射峰推算出,在ＬＢ膜的沉积方向上,十二烷基苯磺酸掺杂的聚苯胺分子的层间距为２９５ｎｍ。     

红外透过、反射吸收光谱研究手性液晶(M1)LB膜的结构与取向

利用ＦＴＩＲ光谱研究了一种手性液晶化合物（Ｍ１）ＬＢ膜的结构与取向,该化合物可以形成稳定的单层与多层膜。手性分子中,芳香环平面向于垂直基片表面,分子中的烷基链部分则与基底表面法线方向成一定的角度。     

功能纳米结构可控生长的新途径:非模板选择性自组装

文章介绍了一种非模板选择性自组装纳米结构的方法.从实验和理论上研究了两种有机分子在Ag单晶不同表面上的吸附行为,发现在Ag（775）基底上PTCDA分子会完全吸附在（111）台阶面上,而DMe-DCNQI分子则完全吸附在（221）台阶面上.该研究还阐明了PTCDA分子与基底原子之间的相互作用机制,提出了PTCDA与基底之间的相互作用是通过分子末端官能团的氧原子实现的,中心的π共轭区域与基底相排斥,理论模拟得到的氧原子的NIXSW相干长度以及碳原子的近边X射线吸收谱与实验结果符合得较好.     

Dy@C82分子在Au(111)表面依赖于覆盖度的取向研究

利用超高真空扫描隧道显微镜, 在低温(80 K)下研究了同分异构体分子Dy@C₈₂在Au(111)表面的吸附与分子取向．在低覆盖度下,Dy@C₈₂分子优先吸附于台阶边缘形成分子团簇与分子链结构．这种吸附取决于分子-衬底的相互作用,并存在多种不同的分子取向．增大分子覆盖度后,Dy@C₈₂在金表面形成二维有序密排的单层膜结构．Dy@C₈₂分子在金表面的取向倾向于其C₂长轴与金表面近乎平行．具有三种取向的分子最具优势,而同种取向的分子组成许多局限于一个个小区域内的取向有序结构畴．随着覆盖度的增加,Dy@C₈₂分子在Au(111)表面趋向于短程有序取向排列,这是由分子-衬底作用与分子间的偶极-偶极作用共同决定的．     

表面增强拉曼光谱研究胞嘧啶在银胶上的吸附行为

为探讨胞嘧啶(Cytosine,Cy)在基底银表面的吸附特性和规律,采用表面增强拉曼散射(SERS)光谱对其吸附行为进行分析,并结合量子化学密度泛函理论(DFT)/B3LYP计算方法对Cy分子的常规拉曼光谱(NRS)及Cy与Ag团簇吸附的SERS光谱进行计算,与测定结果进行比对且对其拉曼峰进行系统指认及归属,理论计算结合实测值探讨了Cy在基底Ag上的增强效应和吸附行为。考察了Cy分子在Ag纳米粒子上的不同吸附时间、浓度、pH等条件对SERS光谱的影响及优化,发现pH影响最大,在中性和强碱性条件下的增强效应明显优于酸性。Cy分子存在2种不同的异构体和3种不同的存在形态,并随酸度变化相互转化而达动态平衡。基于Cy在不同pH时的形态分布和相应的SERS变化规律,结合DFT算得的Cy分子中的电荷分布及在银基底表面的吸附机制,详细探讨了酸碱对Cy分子的SRES光谱影响的内因和吸附机理,指出在中性和弱碱性时,是Cy中的N3和O与Ag形成配位吸附;在pH大于11时,N与Ag形成配位吸附,而O与Ag形成共价吸附。     

H2O分子在Fe（100）, Fe（110）, Fe（111）表面吸附的第一性原理研究

采用第一性原理研究了H₂O分子在Fe（100）,Fe（110）,Fe（111）三个高对称晶面上的表面吸附.结果表明,H₂O分子在三个晶面上的最稳定结构皆为平行于基底表面的顶位吸附结构.H₂O分子与三个晶面相互作用的吸附能及几何结构计算结果表明H₂O分子与三个晶面的相互作用程度不同,H₂O分子与Fe（111）晶面的相互作用最强,其次是Fe（100）,相互作用最弱的是Fe（110）表面,而这与晶面原子 关键词： 第一性原理 Fe单晶表面 2O分子')" href="#">H₂O分子 分子吸附     

导电高聚物的三阶非线性光学效应

最近，导电高聚物作为具有快速响应和大的Ｘ～（３） 的非线性光学材料的希望引超了足够的重视，这是因为它可能在快速光开关、非线性记忆和光晶体管等上获得应用．导电高聚物的三阶非线性光学系数Ｘ～（３），在１０～（－９）─１０～（－１２）ｅｓｕ范围之内，并强烈地依赖于主链结构、高聚物链的构向和取向、共轭长度、取代基种类、掺杂程度和聚合条件等．所观察到的非线性光学效应是本征的，它可能与孤子、极化子和双极化子的光激发有关．本文讨论导电高聚物的三阶非线性光学效应的特性、来源、分子设计、研究进展和展望．     

聚甲基丙烯酸三氟乙酯单体与分子链在金属有机框架中吸附及取向特性的理论研究

本文结合分子动力学、密度泛函理论和蒙特卡洛方法,研究了光学损耗低的氟化聚合物单体分子甲基丙烯酸三氟乙酯（TFMA）及其分子链在[Zn2(BDC)2TED]n和[Zn2(BPDC)2TED]n两种结构有序的金属有机框架（MOFs）材料中的吸附特性,得到相应的吸附数量和取向程度,以探索提高聚合物材料双折射性的有效途径。通过分析结果得出影响TFMA单体分子在这两种MOF孔道中吸附及取向特性的三个因素：a）由于MOF孔道壁是由金属离子和有机配体组成的极性表面,MOF孔壁与极性分子TFMA之间的静电相互作用对TFMA单体分子在孔道内的吸附和取向有促进作用;b）在受限空间中的聚合物单体分子之间的静电相互作用使其分子间隙更加紧密,同样也对其分子取向有促进作用;c）在这个两种孔洞与聚合物单体分子相对大小不同的MOF中,单体分子和分子链的取向度基本一致,但单体分子在孔径较大的MOF中吸附数量更多。这三个因素的重要影响,为聚合物单体或MOF的选取、对聚合物链取向及双折射性的控制提供理论预测方法。     

Role of lateral alkyl chains in modulation of molecular structures on metal surfaces

We use low energy electron diffraction, scanning tunneling microscopy, first-principles density-functional theory, and molecular mechanics calculations to analyze the adsorption and growth of quinacridone derivatives (QA) with alkyl chains of 4 and 16 carbon atoms on a Ag(110) substrate. Surprisingly, we find that the alkyl chains determine the orientation of the molecular overlayers. While the interaction of QA and the Ag substrate is primarily due to chemical bonding of oxygen to the silver substrate, determining the molecular orientation and preferred adsorption site, the intermolecular arrangement can be adjusted via the length of alkyl chains. We are thus able to fabricate uniform QA films with very well controlled physical properties.     

Crystallization of polymer chains induced by graphene： Molecular dynamics study

The present work is devoted to a study of the molecular mechanisms of the crystallization of polymer chains induced by graphene by using molecular dynamics （MD） simulations. From the atomic configuration translation, the number distri- bution of the atoms, and the order parameter S, the crystallization process can be summarized in two steps, the adsorption and the orientation. By analyzing the diffusion properties of the polymer chains, we find that a graphene substrate has a great adsorption for the polymer molecules and the polymer molecules need more time to adjust their configurations. Therefore, the adsorption step and the orientation step are highly cooperative.     

Molecular adsorption and growth of naphthalene films on Ag(1 0 0)

The adsorption of naphthalene, vacuum deposited on a Ag(1 0 0) surface, was comprehensively investigated by means of low-energy electron diffraction (LEED), temperature-programmed thermal desorption (TPD) spectroscopy, X-ray photoelectron spectroscopy (XPS), and polarization-dependent near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in the mono- and multilayer regime. A growth of long-range ordered monolayer at 140 K is observed with LEED. The polarization-dependent C 1s NEXAFS shows that the naphthalene molecules in the monolayer lie almost parallel to the Ag(1 0 0) surface. With increasing film thickness, the molecular orientation turns to upright position. Furthermore, NEXAFS measurements show that in the multilayer regime the molecular orientation depends on the substrate temperature during deposition.     

IR Dichroism of Langmuir–Blodgett Films Based on Fatty Acids

We propose a method of measurement and quantitative estimation of dichroic ratios of submicron laminated Langmuir–Blodgett films by the IR spectra of multiple attenuated internal reflection. The method has been used in calculating the angles of orientation of molecular chains of stearic and palmitic acids in the process of their molecular deposition on an optical substrate. It has been found that in the process of structural self-organization of ensembles the degree of orientation of macromolecules is the higher, the greater the number of links entering into the aliphatic chain.     

SERS studies on 1–4 dihydroxyanthraquinone at Ag electrode

Raman scattering studies on 1–4 dihydroxyanthraquinone (DHAQ) at Ag electrode have been carried out to investigate the enhancement in the spectral line intensity after adsorption. Charge transfer between the adsorbate and the substrate is more pronounced for certain normal modes of vibration. It is found that the DHAQ molecules are lying with their molecular plane on the top of the metal surface. Laser induced fluorescence spectra of DHAQ have also been analysed with a view to assign the relative orientation of absorption and emission dipoles.     

Effect of crystallographic orientations on transport properties of methylthiol-terminated permethyloligosilane molecular junction

The understanding of the influence of electrode characteristics on charge transport is essential in the field of molecular electronics. In this work, we investigate the electronic transport properties of molecular junctions comprising methylthiol-terminated permethyloligosilanes and face-centered crystal Au/Ag electrodes with crystallographic orientations of (111) and (100), based on the ab initio quantum transport simulations. The calculations reveal that the molecular junction conductance is dominated by the electronic coupling between two interfacial metal-S bonding states, which can be tuned by varying the molecular length, metal material of the electrodes, and crystallographic orientation. As the permethyloligosilane backbone elongates, although the σ conjugation increases, the decreasing of coupling induced by the increasing number of central Si atoms reduces the junction conductance. The molecular junction conductance of methylthiol-terminated permethyloligosilanes with Au electrodes is higher than that with Ag electrodes with a crystallographic orientation of (111). However, the conductance trend is reversed when the electrode crystallographic orientation varies from (111) to (100), which can be ascribed to the reversal of interfacial coupling between two metal-S interfacial states. These findings are conducive to elucidating the mechanism of molecular junctions and improving the transport properties of molecular devices by adjusting the electrode characteristics.     

Adsorption of neurotensin‐family peptides on SERS‐active Ag substrates

Kinetensin (KN) and its amino acids 1–8 fragment ([des‐Leu⁹]KN), neuromedin N (NMN), and xenopsin (XP) and its two analogs (XP‐1 and XP‐2) belong to the neurotensin family of peptides and are known to stimulate the growth of human tumors. In this work, we report Fourier transform‐Raman and surface‐enhanced Raman scattering (SERS) studies of these peptides and discuss their structures, orientation, and mode of adsorption onto a highly specific, electrochemically roughened SERS‐active Ag electrode that is characterized by the formation of a 50–150 nm Ag island on its surface. We show that the investigated peptides bind preferentially to this surface by substantial electronic overlap between the metal surface and the π‐orbitals of the benzene rings of the Phe, Tyr, and Trp residues, which forces them to take parallel or almost parallel orientations with respect to the surface. In addition, the –CH₂–, –CNH₂, and –COO^‐ molecular fragments are involved in interactions with (binding to or in close proximity with) the Ag surface. The SERS data show that the adsorption modes in each of these cases are very similar. In addition, we show that the specific differences in the amino acid sequences do not significantly affect the orientation of the investigated peptides on the Ag substrate. This result implies that the N‐termini of the neurotensin‐family peptides do not influence the mode for adsorption onto the Ag substrates. Copyright © 2012 John Wiley & Sons, Ltd.     

一种液晶化合物LB膜中的分子取向及膜结构

"利用LB技术制备出MPUOPM的Langmuir和LB膜．随着表面压力的升高,在?-A曲线上的可观察到一个明显的折点．通过与分子刚性基团的理论截面积相比较,发现该折点反映的是单层膜向多层膜的转变．紫外可见、偏振红外等光谱被用来研究膜的结构,发现烷基链与基片法线夹角为48o,C＝N基团互相平行,与基片法线呈51o夹角排列．"