氢、氮、铍、锂原子在缺陷富勒烯CX（x=58-62）中的吸附与渗透

碳富勒烯包合物由于潜在的应用前景受到广泛关注。我们采用第一性原理方法计算了氢、氮、锂、铍原子在不同碳富勒烯中的吸附和穿越。根据原子在不同碳富勒烯笼中的势能曲线,我们给出了原子穿越碳富勒烯笼的势垒和势阱,归纳出原子穿越碳笼机理分为插入机理、渗透机理以及插入机理和渗透机理的混合机理。     

掺杂B_nN_n(n=12,16,20,24,28)团簇的生成热

中等尺寸的硼氮富勒烯笼与碳笼富勒烯相似,具有纳米尺度的球形内包空间,应该可以形成内包原子的笼状包合物,且无论从理论研究,还是从应用研究上讲都还处于起步阶段.我们采用第一性原理方法计算了第一、二、三、四周期内各元素原子作为M原子,分别构建M@B_nN_n(n=12,16,20)包合物并计算结合能.发现当硼氮富勒烯笼直径较小时,不同元素结合能的大小规律与原子半径的规律相符.副族元素的Mn、Fe、Co和Ni较其它元素的包合物稳定性明显增加.     

氦原子嵌入富勒烯过程的从头算研究

采用从头算方法,利用密度泛函理论(DFT)模拟不同路径、不同压力条件下He@C_(60)的形成过程.通过对He嵌入富勒烯的势垒进行研究发现,He原子进入碳笼最可能的路线是:He原子沿曲线路径靠近碳笼,然后沿六边形中心进入碳笼,并最终停留在碳笼中心.并通过模拟不同压力条件下He原子进入碳笼的势垒大小,简要探讨了合成He@C_(60)的最佳条件.并进一步研究了nHe@C_(60)(n=1,2,3)的反应势垒问题.     

He原子嵌入富勒烯过程的从头算研究

采用从头算方法,利用密度泛函理论（DFT）模拟不同路径、不同压力条件下He@C60的形成过程。 通过对He嵌入富勒烯的势垒进行研究发现,He原子进入碳笼最可能的路线是：He原子沿曲线路径靠近碳笼,然后沿六边形中心进入碳笼,并最终停留在碳笼中心。并通过模拟不同压力条件下He原子进入碳笼的势垒大小,简要探讨了合成He@C60的最佳条件。并进一步研究了nHe@C60(n=1,2,3)的反应势垒问题。     

过渡金属富勒烯化合物V_xC_(60)的Raman光谱

研究了金属富勒烯化合物 Vx C6 0 的 Raman光谱。通过比较不同金属原子含量 ( x=1 .44,2 .65,4.35,1 1 .2 )样品的 Raman光谱 ,发现过渡金属 V的原子与 C原子之间出现键合。当金属含量较高时 ,这种碳笼结构的金属富勒烯化合物转变为金属碳化物。     

内掺过渡金属非典型富勒烯M@C22(M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni) 几何结构、电子结构、稳定性和磁性的密度泛函研究

采用密度泛函理论中广义梯度近似对非典型富勒烯C₂₂和过渡金属内掺衍生物M@C₂₂(M=Sc,Ti,V,Cr,Mn,Fe,Co和Ni)的几何结构和电子结构进行计算研究.发现非典型富勒烯C₂₂的基态结构是含有一个四碳环的单重态笼状结构.过渡金属原子的掺入明显提高了体系的稳定性. C-M键既有一定共价性又有一定离子性.磁性、能级图、轨道分布和态密度图分析表明: M原子的3d轨道和碳笼的C原子的原子轨道之间存在较强的轨道杂化. Ti, Cr, Fe和Ni内掺的结构出现磁性完全猝灭现象. Sc和碳笼间是弱反铁磁作用, V,Mn和Co与碳笼间是弱铁磁作用.     

双磁性中心内嵌富勒烯Y_2C_2@C_(82)-C_2(1)中的超快自旋动力学行为

自旋翻转和自旋转移是实现基于内嵌富勒体系自旋逻辑功能器件设计的先决条件.本文以双磁性中心内嵌富勒烯Y_2C_2@C8_2-C_2(1)体系为例,采用第一性原理计算方法,结合Λ进程理论模型和自编的遗传算法程序,在该内嵌富勒烯体系中分别实现了亚皮秒时间尺度内的自旋翻转和自旋转移过程.计算结果表明,优化后的内嵌Y_2C_2团簇结构和实验得到的各项数据基本吻合,并且会对外部的C8_2-C_2(1)笼结构产生一定的排斥力,但由于富勒烯笼状结构具有很强的稳定性,所以整个体系仍然保持碳笼结构的完整性.通过对自旋密度分布与激光脉冲作用下自旋期望值演化的具体分析,经由Λ进程的自旋翻转是基于两个Y元素的整体自旋翻转;自旋转移则源自两个磁性中心以及碳笼之间在激光脉冲作用下的自旋密度重新分布.本文结果揭示了Y_2C_2@C8_2-C_2(1)体系中的超快自旋动力学机理,可望为基于实际内嵌富勒烯分子的自旋逻辑功能器件设计提供理论依据.     

2004年第5期《物理》内容预告

研究快讯能量与空间分辨的单分子显微术———透过碳笼“看”富勒烯　包合物内的金属原子(王炜华等) ;绝对测量He原子快电子碰撞双激发的电子关联动力学(刘　小井等) .评述半导体量子点及其应用(Ⅱ) (赵凤瑷等) .前沿进展光子晶体光纤及其应用(赵玲慧等) ;GeSbTe与AgInSbTe体系     

利用扫描隧道显微镜表征和操纵单分子

扫描隧道显微镜（STM）提供给我们一种表征单分子的局域物理和化学特性的特殊方法，甚至还能帮助我们操纵单分子以构造分子尺度的新型器件。本文中我们采用了两种新型STM技术分别来表征封装在富勒烯笼里面的金属原子和构造一种具有较强Kondo效应的分子器件。空间dI/dV映像谱被用来探索单个Dy@C82分子中能量分辨的金属-笼杂化态，揭示了有关Dy原子在碳笼中的空间位置和Dy-碳笼之间相互作用的重要信息。我们也通过控制STM针尖诱导的高电压脉冲来诱导CoPc分子的边缘脱氢化，从而改变了这个分子在Au(111)表面的吸附构型，导致吸附在Au表面的完整CoPc分子所不具备的Kondo效应产生。     

C36——富勒烯固体中最小的成员

在一定条件下,碳原子能够形成相对稳定的中空笼形分子．这些分子具有不同的碳原子数,如Ｃ３６,Ｃ５０,Ｃ６０和Ｃ７０等,它们被统称为富勒烯（ｆｕｌｅｒｅｎｅｓ）．制备单一尺寸笼形碳分子固体是人们所特别关心的,因为只有这样,才有可能对某种尺寸的富勒烯作出全...     

Photoionization of Endohedral Atoms in Fullerene Cages

The finite-element discrete variable representation combined with the method of complex coordinate rotation is implemented to investigate the hydrogenic atoms and alkali metals encapsulated by the fullerene cages. The energy levels varying with the confining potential of the fullerene cage exhibit avoided crossings caused by the so-called mirror collapse from the switch of near degenerate states. The effects of fullerene cages on photoionization of confined atoms leading to the oscillation behavior and confinement resonances in photoionization cross sections are demonstrated. The results of cross sections for hydrogen-like lithium ion as a function of the cage radius and shell thickness are presented. The emergence of the Cooper minima due to the influence of the fullerene cages is observed for endohedral lithium and sodium atoms. Comparisons are made to the existing predictions.     

Some novel plane trajectories for carbon atoms and fullerenes captured by two fixed parallel carbon nanotubes

The movement of atoms and molecules at the nanoscale constitutes a fundamental problem in physics, especially following the motion of atoms in many-body systems condensing together to form molecular structures. A number of simplified nanoscale dynamical problems have been analyzed and here we investigate the classical orbiting problem around two centers of attraction at the nanoscale. An example of such a system would be a carbon atom or a fullerene orbiting in a plane which is perpendicular to two fixed parallel carbon nanotubes. We model the van der Waals forces between the molecules by the Lennard-Jones potential. In particular, the total pairwise potential energies between carbon atoms on the fullerene and the carbon nanotubes are approximated by the continuous approach, so that the total molecular energy can be determined analytically. Since we assume that such interactions occur at a sufficiently large distance, the classical two center problem analysis is legitimate to determine various novel trajectories of the atom and fullerene numerically. It is clear that the oscillatory period of the atom for some bounded trajectories reaches terahertz frequencies. We comment that the continuous approach adopted here has the merit of a very fast computational time and can be extended to more complicated structures, in contrast to quantum mechanical calculations and molecular dynamics simulations.     

Real time microscopy, kinetics, and mechanism of giant fullerene evaporation

We report in situ high-resolution transmission electron microscopy observing the shrinkage of single-layer giant fullerenes (GF). At temperatures approximately 2000 degrees C, the GF volume reduces by greater than one 100-fold while the fullerene shell remains intact, evolving from a slightly polygonized to a nearly spherical shape with a smaller diameter. The number of carbon atoms in the GF decreases linearly with time until the small subbuckyball cage opens and rapidly disappears. Theoretical modeling indicates that carbon atoms are removed predominantly from the weakest binding energy sites, i.e., the pentagons, leading to the constant evaporation rate. The fullerene cage integrity is attributed to the collective behavior of interacting defects. These results constitute the first experimental evidence for the "shrink-wrapping" and "hot-giant" fullerene formation mechanisms.     

Long fine single-wall carbon nanotube growth by Nano-spin-threading: model schematics and simulations

We have investigated model schematics for a long fine single-wall carbon nanotube growth inside a larger diameter nanotube. Our proposed schematics are as follows: fullerenes are encapsulated into the nano-channel connected with fullerene storage tank; and then a inner nanotube grows via fullerene coalescence under 1200 °C in the nano-channel. Then the grown carbon nanotube is extracted from the nano-channel by mechanical control. We have investigated fullerene mergence inside single-wall carbon nanotube using classical molecular dynamics simulations based on the Tersoff–Brenner potential and the Lennard–Jones potential. During fullerene-encapsulating, since the fullerenes naturally have the kinetic energies due to the suction force and can be also accelerated by external force fields to improve the fullerene encapsulation rate, they can be migrated toward the other side of the nano-channel with kinetic energies. Our molecular dynamics simulations showed that the structural relaxation of dynamically free atoms affected on the growth of inner carbon nanotube rather than the Stone-Wales transformations. Since the broken bonds make the structural relaxation during merging to be easily achieved from the migration of carbon atoms or carbon chains, the inner nanotube grows via the re-bonding-reactions of dynamically free carbon atoms or chains as well as the Stone-Wales transformations. We could conclude that the growth rate of the inner CNT could be increased when bond-breakings between carbon atoms of fullerenes were easily achieved.     

富勒烯C20四聚体的结构与性能研究

采用密度泛函理论(DFT)中的杂化密度泛函(B3LYP)方法, 在6-31 G基组水平上对C₂₀四聚体进行了几何参数全优化, 得到了基态构型, 并对其稳定性、电子结构、极化率和芳香性进行了计算研究. 结果表明: C₂₀碳笼以[2+2]加成方式结合形成C₂₀四聚体, 具有良好的热力学稳定性; C原子内部以sp²的方式杂化, C原子之间有少量电荷转移; C₂₀ 四聚体的IR和Raman光谱都有较多的振动峰; 随碳笼数的增加, C₂₀聚合物中原子间的成键相互作用随之增强; C₂₀四聚体具有芳香性.     

Metal atom catalyzed enlargement of fullerenes

A metal catalyzed enlargement of fullerenes has been demonstrated by in situ high-resolution transmission electron microscopy. It was found that carbon atoms and clusters can be continuously incorporated into a closed fullerene cage at a high temperature, leading to an increase in the diameter and consequently the formation of giant fullerene with the assist of adsorbed metal atoms. Density functional theoretical simulations indeed suggest that the activation energy for the carbon incorporation and the associated Stone-Wales transformation can be substantially reduced due to the presence of metal atoms, which should be of key importance for the fullerene growth.     

Defect-induced ferromagnetism in fullerenes

Based on the ab initio electronic structure calculations the picture of ferromagnetism in polimerized C₆₀ is proposed which seems to explain the whole set of controversial experimental data. We have demonstrated that, in contrast with cubic fullerene, in rhombohedral C₆₀ the segregation of iron atoms is energetically unfavorable which is a strong argument in favor of intrinsic character of carbon ferromagnetism which can be caused by vacancies with unpaired magnetic electrons. It is shown that: (i) energy formation of the vacancies in the rhombohedral phase of C₆₀ is essentially smaller than in the cubic phase, (ii) there is a strong ferromagnetic exchange interactions between carbon cages containing the vacancies, (iii) presence of iron impurities can diminish essentially the formation energy of intrinsic defects, and (iv) the fusion of the magnetic single vacancies into nonmagnetic bivacancies is energetically favorable. The latter can explain a fragility of the ferromagnetism.     

Interatomic Interaction at the Aluminum–Fullerene C60 Interface

Journal of Experimental and Theoretical Physics - We propose a model of interaction between aluminum and carbon atoms at the Al/C60 interface. The binding energy and the fullerene position of the...     

Fullerenes with symmetrically arranged defects: Geometry and electronic structure

Recently, fullerene structures with symmetrically arranged pairs of pentagonal-heptagonal defects were proposed to explain the round shape of giant multilayer fullerene cages. Even though those proposed cages are defective, they belong to the icosahedral point group. Using the Tersoff-Brenner potential, we calculated the shape of the defective fullerenes. It is found that these fullerenes have a rounder shape than structures without defects. The electronic structure of the fullerenes with defects is also calculated within the Hückel approach. The electronic structures are closed and the energy gaps between bonding and antibonding orbitals are higher than those for fullerenes with no defects in almost all cases considered.