Preferable Orientations of Interacting C_(60) Molecules inside Single Wall Boron Nitride Nanotubes

This work focuses on the preferable orientation analysis of the hybrid system where the Ceo molecules are encapsulated inside the boron nitride nanotubes by using the two-molecule model.The low-energy state can be acquired in the contour map,which provides the visual information of the systematical van der Waais interaction potential for the Ceo molecules adopting different orientations.Our results show that the C_(60) molecules exhibit the preferred pentagon and hexagon orientations with the tube's diameter smaller and larger than 13.55 A,respectively.The preferred two-bond orientation obtained in the single-molecule model is absent in this study,indicating that the intermolecular interaction of adjacent C_(60) molecules plays an important role in the orientational behaviors of this peapod structure.     

六边形晕斑图等离子体参数的光谱测量

在空气与氩气按比例混合组成的气体放电中,研究了由中心点和六边形晕组成的六边形晕斑图。从照片中观察六边形晕斑图结构,发现中心点和六边形晕的亮度有明显的差异,说明中心点和六边形晕可能处的等离子体状态不同。利用发射光谱法,详细研究了该六边形晕斑图结构的中心点和六边形晕的等离子体参数随压强的变化关系。实验根据氮分子第二正带系(C3Π_u→B3Π_g)谱线计算了中心点和六边形晕的分子振动温度;通过氮分子离子(391.4 nm) 与氮分子(394.1nm)谱线强度比,反映中心点和六边形晕的电子平均能量;利用氩原子696.5 nm(2P₂→1S₅)谱线的展宽,研究了电子密度。实验结果表明： 六边形晕斑图主要范围是氩气含量从60%～75%、压强从30～46 kPa。在相同的压强条件下,六边形晕比中心点的分子振动温度、电子平均能量均要高。随着压强从30 kPa逐渐升高到46 kPa,中心点和六边形晕的分子振动温度、电子平均能量是逐渐增大的。在相同的压强条件下,六边形晕比中心点的谱线展宽要大,且随着压强的升高而增加,表明电子密度随着压强的增大而升高。六边形晕和中心点的等离子体的状态不同,说明二者放电机制上的差异。进一步采用高速照相机对斑图的电流脉冲进行分脉冲瞬时拍摄,发现中心点是由先放电的体放电形成,而六边形晕是由放电晚于体放电的沿面放电形成。     

Interaction of alkanethiols with single-walled carbon nanotubes: First-principles calculations

We report the results of our first-principles study based on density functional theory on the interaction of alkanethiols with both defected and defect-free single-walled carbon nanotube (SWCNT). The adsorption energies are calculated for various configurations such as alkanethiol molecule approaching to defect sites heptagon, hexagon, and pentagon in defective tube, and another case where the alkanethiol approaching to hexagon in defect-free nanotube. The calculated results showed that alkanethiols are rather strongly bound to the outer surface of both the defected and defect-free carbon nanotubes with the binding energy of about −50.58 kcal/mol, consistent with the experimental result. We also find that alkanethiols prefer to be adsorbed on the hexagon ring site of defect-free nanotube. Furthermore, the effect of alkanethiols chain length on the adsorption of alkanethiols on carbon nanotubes has been investigated, and the obtained results reveal that the longer alkanethiols bind rather more strongly to the nanotube surface.     

Self-assembly of C60 fullerenes on quasi-one-dimensional Si(111)4 × 1-In surface

Using scanning tunneling microscopy observations, self-assembly of C₆₀ fullerenes in the course of room-temperature adsorption onto Si(111)4 × 1-In reconstruction and after subsequent annealing at temperatures ranging from 150 to 450 °C has been studied. Adsorbed C₆₀ fullerenes have been found to occupy off-centered positions on In-atom rows forming linear chains with a maximal length of eight C₆₀ molecules. Intermolecular spacing within the regular chains equals three lattice constants of Si(111) surface. Two energetically different adsorption states of C₆₀ have been detected, one of which is occupied preferentially at room temperature, while occupation of the second (more tight) state dominates at temperature above ~ 150 °C. In the first state, C₆₀ fullerene resides plausibly in a continuous rotation, while in the second state a C₆₀ molecule is fixed tightly in a single orientation with a C₆₀ hexagon pointing upward. Transition of C₆₀ fullerenes to the more stable state is accompanied by expelling In atoms from the Si(111)4 × 1-In reconstruction.     

Interaction of Methane with Single-Walled Carbon Nanotubes： Role of Defects,Curvature and Nanotubes Type

We investigate the interaction of single-walled carbon nanotubes （SWCNTs） and methane molecule from the first principles. Adsorption energies are calculated, and methane affinities for the typical semiconducting and metallic nanotubes are compared. We also discuss role of the structural defects and nanotube curvature on the adsorption capability of the SWCNTs. We could observe larger adsorption energies for the metallic CNTs in comparison with the semiconducting CNTs. The obtained results for the zig zag nanotubes with various diameters reveal that the adsorption energy is higher for nanotubes with larger diameters. For defected tubes the adsorption energies are calculated for various configurations such as methane molecule approaching to the defect sites pentagon, hexagon, and heptagon in the tube surface. The results show that the introduce defects have an important contribution to the adsorption mechanism of the methane on SWNTs.     

Anisotropic packing and one-dimensional fluctuations of C60 molecules in carbon nanotubes

The confinement of a C60 molecule encapsulated in a cylindrical nanotube depends on the tube radius. In small tubes with radius RT approximately < 7 A, a fivefold axis of the molecule coincides with the tube axis. The interaction between C60 molecules in the nanotube is then described by a O2-rotor model on a 1D liquid chain with coupling between orientational and displacive correlations. This coupling leads to chain contraction. The structure factor of the 1D liquid is derived. In tubes with a larger radius the molecular centers of mass are displaced off the tube axis. The distinction of two groups of peapods with on- and off-axis molecules suggests an explanation of the apparent splitting of Ag modes of C60 in nanotubes measured by resonant Raman scattering.     

Tunneling magnetoresistance of C2H2 molecules sandwiched between Co clusters

The tunneling magnetoresistance (TMR) of samples containing well-defined Co clusters (≈4.5 nm mean diameter) embedded in C₂H₂ matrices essentially is independent of Co-cluster volume fraction v_Co and reveals a value of about 26% at T=2 K. This result is in contrast to that obtained for Co clusters embedded in C₂H₄ matrices (Phys. Rev. B 67 (2003) 094433). In the latter system the TMR strongly decreased with increasing v_Co indicating different possible orientation of the C₂H₄ molecule sandwiched between the Co clusters. We, therefore, conclude that the C₂H₂ molecules are sandwiched in a rather well-defined orientation between the Co clusters. They probably form double layers of C₂H₂ molecules with the C–C bond axis parallel to the Co cluster surface.     

温度对氨基苯甲酸在粗糙银表面上行为的影响

本文同时测定了当温度从－１９０℃上升到３０℃和从３０℃下降到－１９０℃对氨基苯甲酸（ｐ－Ａｍｉｎｏｂｅｎｚｏｉｃ Ａｃｉｄ，ＰＡＢＡ）和邻氨基苯甲酸（ｏ－Ａｍｉｎｄｂｅｎｚｏｉｎ Ａｃｉｄ，ＯＡＢＡ）在粗糙的银表面上的表面增强拉曼光谱的变化。结果表明，若吸附质表面拉曼光谱的增强主要表现为化学机理，且整个分子平躺在表面，则分子在表面上的取向不会随温度的变化而改变。而温度的变化会引起基于电磁场增强机理     

C60-糖皮质激素荧光特性研究

C60及其衍生物的荧光特性的研究是富勒烯科学领域的一个重要分支.研究了C60-糖皮质激素类衍生物的荧光性质,发现室温下用350 nm波长的光激发,C60-糖皮质激素类衍生物在447 nm处有荧光发射.由于C60分子中60个碳原子是等价的,属Ih群,呈高度对称性,因而同样条件下难以观测到荧光.而C60-糖皮质激素类衍生物在形成的过程中分子结构的对称性发生了改变,使得这类化合物可以在一定波长光的激发下发射荧光.此外,通过对系列浓度(10～130 μmol·L-1)的C60-糖皮质激素氯仿溶液的荧光测定,发现这类化合物存在荧光浓度自猝灭现象,10～64 μmol·L-1浓度范围内,荧光强度随浓度的增大而逐渐增大,大于64 μmol·L-1时荧光强度随浓度的增大而逐渐降低.     

Molecular hydrogen and oxygen interactions with armchair Si nanotubes

Molecular hydrogen and oxygen adsorptions on a (6, 6) armchair silicon nanotube have been studied by optimizing the distances of the admolecules from both inside and outside the tube. Full geometry and spin optimizations have been performed without any symmetry constraints with an all electron 3-21G* basis set and the B3LYP functional. The molecule is originally placed perpendicular or parallel to the tube axis. Hydrogen adsorption with the molecular axis aligned parallel to the surface of the nanotube is less favorable. Hydrogen molecule does not dissociate while oxygen molecule dissociates after optimization. The on-top site is the only preferred site for hydrogen molecule with an adsorption energy of 3.71 eV and an optimized distance of 3.31 for external adsorption whereas the on-top site is the most preferred site with adsorption energy of 3.69 eV for internal adsorption. For oxygen, the molecule dissociates and the most preferred sites are the two bridge sites with an adsorption energy of 9.64 eV, the optimized distance being 1.65/1.68 Å when it is adsorbed from the outside of the tube. When oxygen molecule is originally placed at on-top site it will hold as a molecule after adsorption with a slightly increased bond length. For the internal adsorption of oxygen, the molecules also dissociate in most cases and the zigzag bridge site is the most preferred site. After molecular adsorption for both hydrogen and oxygen, the buckling of the nanotubes increased. Frustration effects in the nanotube due to molecular adsorption are also noted.     

碳纳米管中封装富勒烯的机理

利用经典分子动力学模型,发现C60进入单壁碳纳米管(SWNTs)形成(C60)n@SWNTs的吸入和俘获机理.揭示了吸入和俘获势垒只局域于SWNTs的管口区,而在SWNTs的管内区,C60沿管轴方向的运动几乎不受力.最后,系统地计算了吸入和俘获势垒随SWNTs管径的变化,发现只有当SWNTs的管径大于阈值1238nm时才能吸入C 关键词： 富勒烯相关材料 碳纳米管 类虹吸作用     

基于AgI2-缔合微粒共振散射效应测定阳离子表面活性剂

在pH 3.5 NaAc-HCl介质中,Ag 与过量的I-形成可溶性AgOI2-;当十六烷基三甲基溴化铵(CT-MAB)与AgI2-共存时形成粒径为700 nm的(CTMA-AgI2)n缔合微粒,在360 nm处产生一个共振散射峰,在470 m处产生一同步散射峰.CTMAB浓度cCTMAB在2.0～50.0×10-7mol·L-1范围内与散射光强度I360nm呈线性关系,回归方程为I360nm=2.03×107 cCTMAB 0.48,相关系数r为0.998 5,检出限为8.0×10-8mol·L-1.据此建立了一个测定阳离子表面活性剂含量的共振散射光谱法,用于水样分析,结果满意.共振散射光谱和激光散射研究表明,CTMAB 与AgI2-可通过静电力形成疏水性的CTMA-AgI2缔合物分子,该缔合物分子自动聚集形成稳定的(CTMA-AgI2)n缔合微粒.由于该缔合微粒仅在360 nm处产生共振散射效应,故体系呈乳白色.     

团簇六边形斑图等离子体参数的光谱测量

在氩气和空气混合气体介质阻挡放电中,首次发现了团簇六边形斑图。运用发射光谱法,研究了此斑图中单个团簇的三种等离子体参数：分子振动温度、分子转动温度以及电子的平均能量随空气含量的变化。实验通过测量氮分子光谱并采用氮分子第二正带系(C3Π_u→B 3Π_g)计算了振动温度;同时采集氮分子离子(N+₂)的第一负带系(B 2Σ+_u→X 2Σ+_g)计算转动温度。利用氮分子离子391.4 nm和激发态的氮分子337.1 nm两条发射谱线的相对强度之比,作为研究电子平均能量的变化的依据。结果显示,当混合气体中空气含量从16%逐渐增大到24%时,三种等离子体参数均逐渐增大。     

腺嘌呤、嘌呤和四并苯的表面增强拉曼光谱随温度的可逆变化

用硝酸腐蚀法处理得到了具有表面增强拉曼光谱 (SERS)活性的银表面。在表面温度于 - 1 90℃～30℃变化时 (上升和下降 ) ,分别测定了吸附在银表面上的腺嘌呤、嘌呤和四并苯的表面增强拉曼光谱 ,观察到一系列有关拉曼峰频率和强度的可逆变化。结果表明 ,温度降低 ,吸附分子SERS中受电磁增强机制作用的振动的拉曼位移发生蓝移 ,同时峰强度也有变化 ;而受化学增强机制作用的振动的拉曼位移则不受温度的影响。温度的变化导致分子平面可弯曲分子在金属表面的取向发生变化 ,如腺嘌呤和嘌呤在高温下取直立态 ,而平面的对称分子 (如四并苯 )在表面上的取向则不受温度的影响。     

Pyroelectric nano-rods grown inside alumina nano-pores

This paper reports the formation and properties of nano-composite pyroelectric thin films. They consist of pyroelectric triglycine sulfate (TGS) single-crystal nano-rods grown inside a highly dense array of alumina pores (about 65 nm diameter and density of 1011 cm⁻²). The nucleation and growth of the TGS single crystals are obtained by precipitation from a supersaturated aqueous solution. Nucleation is preferred only at the bottom of the pores due to a tight control of temperature, composition and pore diameter. Growth of single crystals with preferred crystallographic orientation is obtained with the aid of an applied electric field. Various crystallographic orientations (1 0 0) (−1 1 0) (−1 2 0) are obtained separately as a single preferred orientation by changing the amplitude of the electric field during crystal growth. The films exhibit ferroelectric behavior.     

碳纳米管阵列水渗透性质的研究

碳纳米管阵列组成的碳纳米管分子膜在生物学分子器件等方面有重要应用. 本文利用分子动力学方法计算研究水分子对(11, 11)碳纳米管阵列的渗透过程. 结果发现, 只有当阵列间隙面积大于57.91 Ų时, 水分子才能进入阵列间隙中, 并揭示了碳管内部、阵列间隙内水分子结构随相邻碳管间距变化的演化趋势以及管内外水分子电偶极矩的分布特性.     

Standing or lying C70s encapsulated in carbon nanotubes with different diameters

Single-walled carbon nanotubes (SWNTs) encapsulating C₇₀s, so-called C₇₀ peapods, were synthesized in high yield by a vapor-phase doping method. Raman spectra, high resolution transmission electron microscopy (HRTEM), and selected area electron diffraction (SAED) measurement indicate that the tube diameter is one of the important factors to determine the orientation of C₇₀ molecules inside the SWNTs. SWNTs with different diameters give different alignment of C₇₀ molecules. The lying orientation is favorable over the standing orientation in thin nanotube, i.e. 1.36 nm nanotubes, whereas the standing orientation is favorable in thick nanotubes, i.e. 1.49 and 1.61 nm nanotubes.     

Electronics and Structural Properties of Single-Walled Carbon Nanotubes Interacting with a Glucose Molecule：ab initio Calculations

The adsorption of glucose molecule on single-walled carbon nanotubes (SWCNTs) is investigated by density functional theory calculations. Adsorption energies and equilibrium distances are evaluated, and glucose binding to the typical semiconducting and metallic nanotubes with various diameters and chirality are compared. We also investigated the role of the structural defects on the adsorption capability of the SWCNTs. We could observe larger adsorption energies for the larger diameters semiconducting CNTs, while the story is paradoxical for the metallic CNTs. The obtained results reveal that the adsorption energy is significantly higher for nanotubes with higher chiral angles. Finally, the adsorption energies are calculated for defected nanotubes for various configurations such as glucose molecule approaching to the pentagon, hexagon, and heptagon sites in the tube surface. We find that the respected defects have a minor contribution to the adsorption mechanism of the glucose on SWNTs. The calculation of electron transfers and the density of states supports that the electronic properties of SWCNTs do not change significantly after the gluycose molecular adsorption. Consequently, one can predict that presence of glucose would neither modify the electronic structure of the SWCNTs nor direct to a change in the conductivity of the intrinsic nanotubes.     

Electronics and Structural Properties of Single-Walled Carbon Nanotubes Interacting with a Glucose Molecule: ab initio Calculations

The adsorption of glucose molecule on single-walled carbon nanotubes(SWCNTs)is investigated by density functional theory calculations.Adsorption energies and equilibrium distances are evaluated,and glucose binding to the typical semiconducting and metallic nanotubes with various diameters and chirality are compared.We also investigated the role of the structural defects on the adsorption capability of the SWCNTs.We could observe larger adsorption energies for the larger diameters semiconducting CNTs,while the story is paradoxical for the metallic CNTs.The obtained results reveal that the adsorption energy is significantly higher for nanotubes with higher chiral angles.Finally,the adsorption energies are calculated for defected nanotubes for various configurations such as glucose molecule approaching to the pentagon,hexagon,and heptagon sites in the tube surface.We find that the respected defects have a minor contribution to the adsorption mechanism of the glucose on SWNTs.The calculation of electron transfers and the density of states supports that the electronic properties of SWCNTs do not change significantly after the gluycose molecular adsorption.Consequently,one can predict that presence of glucose would neither modify the electronic structure of the SWCNTs nor direct to a change in the conductivity of the intrinsic nanotubes.     

不同结构六边形斑图演化过程光谱特性

采用发射光谱法,研究了水电极介质阻挡放电中具有相同对称性的3种不同结构的六边形斑图演化过程的光谱特性。实验结果表明,随着外加电压的增加,放电首先形成六边形点阵斑图,然后是空心六边形斑图,最后是蜂窝六边形斑图。利用氩原子696.5 nm(2P_2→1S_5)谱线的展宽、氩原子763.2 nm(2P_6→1S_5)与772.1 nm(2P_2→1S_3)两条谱线强度比法和氮分子第二正带系(C~3Π_u→B~3Π_g)的发射谱线,研究上述3种斑图的电子密度、电子激发温度及分子振动温度。结果发现,随着外加电压的升高,六边形点阵斑图、空心六边形斑图和蜂窝六边形斑图的电子密度逐渐减小,而电子激发温度和分子振动温度逐渐增加。等离子体状态的改变直接影响着斑图的自组织。