ELECTRONIC-STRUCTURES OF THE ALKALI-CONTAINING BUCKMINSTERFULLERENES (A-DELTA-C60) (A=LI,NA,K,RB,CS) AND THE HALOGEN-CONTAINING BUCKMINSTERFULLERENES (H-DELTA-C60) (H=F,CL,BR,I)

The geometrical parameters and electronic structures of C60, (A partial derivative C60) (A = Li, Na, K, Rb, Cs) and (H partial derivative C60) (H = F, Cl, Br, I) have been calculated by the EHMO/ASED (atom superposition and electron delocalization) method. When putting a central atom into the C60 cage, the frontier and subfrontier orbitals of (A partial derivative C60) (A = Li, Na, K, Rb, Cs) and (H partial derivative C60) (H = F, Cl) relative to those of C60 undergo little change and thus, from the viewpoint of charge transfer, A (A = Li, Na, K, Rb, Cs) and H (H = F, Cl) are simply electron donors and acceptors for the C60 cage resPeCtively. Br is an electron acceptor but it does influence the frontier and subfrontier MOs for the C60 cage, and although there is no charge transfer between I and the C60 cage, the frontier and subfrontier MOs for the C60 cage are obviously influenced by I. The stabilities DELTAE(X) (DELTAE(X) = (E(X) + E(C60)) - E(x partial derivative C60)) follow the sequence I < Br < None < Cl < F < Li < Na < K < Rb < Cs while the cage radii r follow the inverse sequence. The stability order and the cage radii order have been explained by means of the (exp-6-1) potential.

Theoretical studies of the C60 and alkali metal-containing complexes C60 M

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纳秒激光诱导C60分子碎裂中轻碎片离子C+n(n＜30)的产生机理研究

The time of flight mass spectrometric technique was used to determine the initial mean kinetic energy of small fragment ions C-n(+) (n <= 11) produced from C-60 excited by 532 nm nanosecond laser pulses. The measured kinetic energy shows little variation with the fragment mass and the laser fluence in a broad range. Based on the assumption that C-30(+) is produced predominantly by a single electron emission followed by successive C-2 evaporation from hot C-60 in the nanosecond laser field, the formation of small fragments is interpreted as the complete breakup of the unstable C-30(+) cage structure. The interpretation is consistent with the previously observed results.

气相C60在纳秒激光场中的内能分布以及退激研究

本工作建立了激光飞行时间质谱仪，与示波器获取质谱全图技术联合运作，研究了气相C60分子在具有不同空间分布的纳秒激光场中的内能分布规律以及退激产物的分布特征。研究表明，C60分子的内能分布在较低内能区遵循幂指数衰减形式E-b，并且幂指数值b随激光场发散度的增加而增加；在较高内能区的内能分布迅速偏离各自对应的幂指数规律。实验结果与把激光束和分子束看作高斯分布的理论预言符合的很好。对碎片质谱的研究表明，质谱具有明显的双峰分布特征，且激光通量较低时，碎片表现出明显的幻数结构，随着激光通量的增加，幻数结构在质谱中逐渐消失。碎片离子的产额分布表明，激光场的发散度越大，C60分子的碎裂程度随激光通量变化趋势就越快；分析轻碎片离子的峰形分布得到，所有轻碎片离子具有相同的平均初始动能；在近似认为富勒烯离子蒸发一个C2分子具有相同的动能释放的情况下，得到该动能释放值约为0.40±0.02eV。不同激光场中延迟电离与非延迟电离的产额分布表明，激光场发散度越大，两种电离成分随激光通量变化趋势越快，延迟电离成分占总电离成分的百分比越高。通过分析不同激光场中延迟电离离子飞行质谱，实验测量C60分子蒸发中性C2对应的蒸发势垒为10.59±0.17eV

重离子在C60薄膜中引起的辐照效应研究

本项工作选择了不同种类、不同电荷态的从低能到高能的多种荷能重离子，对C60薄膜进行了辐照。并且通过多种分析测试手段（Raman、FTIR、XPS、AFM）分析了荷能重离子在C60薄膜中的辐照效应，并对机理进行了研究。同时也研究了低能B离子在碳的三种同素异构体：石墨、金刚石和C60中引起效应的差异。对于以弹性碰撞为主导的低能区，用170keV B离子辐照了碳的三种同素异构体，并从这些辐照样品的Raman谱数据演绎出了C60、金刚石和石墨的损伤截面σ。首次在完全相同的辐照条件下，研究了碳的三种同素异构体对辐照的敏感性和结构稳定性的差异，研究结果表明：C60对B离子辐照的敏感性最强，金刚石次之，相比之下石墨在B离子辐照下结构最为稳定，而且在辐照过程中，随辐照量的增加三种靶材料遭破坏的程度截然不同，表明它们的辐照敏感性差异随辐照量而变化。由XPS谱得知，在最高辐照量下石墨的sp2 C转变不多；而金刚石的sp3 C基本转变成了sp2 C。再次证明在B离子辐照下石墨的结构最为稳定。随着170keV B离子辐照量的增加，C60薄膜的FTIR和Raman谱中各激活模的强度都有不同程度的衰减，最终消失，即C60分子完全被破坏。在B离子的辐照下，C60分子的不同红外激活模和Raman激活模的辐照敏感性和结构稳定性也有差异：在C60分子的4个红外激活模中，T1u(4)对辐照最为敏感，而T1u(2)最为稳定。并率先确定了明显可见的5个Raman激活模对辐照的敏感性和结构稳定性的差异，其中Hg(4)对辐照最敏感，而Hg(3)最稳定。在以非弹性碰撞为主导的高能区，用2.15GeV的Kr离子辐照了多层堆叠的C60样品，辐照样品的分析结果表明：在相同能量或相同电子能损下，C60分子的辐照损伤随辐照量的增加趋于严重；而在相同辐照量下，C60的损伤程度随电子能损的增加而增强；但C60分子的损伤在某居中的电子能损值和辐照量下有一定的恢复。在电子能损相同或相近时，速度较低的Kr离子对C60分子的损伤更为严重，揭示了团簇材料的快重离子损伤建立过程中的离子速度效应。为了研究低速高电荷态离子在C60薄膜中引起的辐照效应，用不同电荷态的Xe离子辐照了C60薄膜。由AFM形貌图可知，不同电荷态Xe离子辐照C60薄膜，使其表面形貌发生了不同程度的改变。其粗糙度随着辐照Xe离子电荷态的不断增加而不断减小

Negative differential resistance and memory effect in diodes based on 1,4-dibenzyl C60 and zinc phthalocyanine doped polystyrene hybrid material

Negative differential resistance (NDR) and memory effect were observed in diodes based on 1,4-dibenzyl C60 (DBC) and zinc phthalocyanine doped polystyrene hybrid material. Certain negative starting sweeping voltages led to a reproducible NDR, making the hybrid material a promising candidate in memory devices. It was found that the introduction of DBC enhanced the ON/OFF current ratio and significantly improved the memory stability. The ON/OFF current ratio was up to 2 orders of magnitude. The write-read-erase-reread cycles were more than 10(6), and the retention time reached 10 000 s without current degradation.

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Molecular dynamics simulation of observed c(4x4) and c(4x3) C60 alignments on the Si(100) reconstructed surface.

We have implemented a large-scale classical molecular dynamics simulation at constant temperature to provide a theoretical insight into the results of a recently performed experiment on the monolayer and multi-layer formations of molecular films on the Si(100) reconstructed dimerized surface. Our simulation has successfully reproduced all of the morphologies observed on the monolayer film by this experiment. We have obtained the formation of both c(4 4) and c(4 3) structures of the molecules and have also obtained phase transitions of the former into the latter.

Modelling the adsorption and imaging of C60 molecules on a graphite substrate

The adsorption of a C60 monolayer on a graphite substrate was modelled via molecular dynamics simulation covering a significant period of 160 picoseconds. The final configuration of C60s agrees closely with that observed in a scanning tunnelling microscopy (STM) experiment. Clusters of adsorbed molecules were then selected and their STM-like images were computed via the Keldysh Green function method.

Observation of C60 film formation on a highly oriented pyrolitic graphite substrate via scanning tunnelling microscopy

We have investigated the early stages in the adsorption process of C60 molecules on a highly oriented pyrolitic graphite (HOPG) substrate. C60 powder was thermally evaporated in UHV of 10−8 Pa conditions onto a freshly cleaved HOPG surface. We did not observe individual fullerenes on the substrate for the case of short deposition times and low evaporation rates. However, small islands of C60 molecules with an fcc structure could be observed when the deposition rate was about 0.2 nm/min and the total thickness was above 1 nm. The islands did not grow in the vicinity of the HOPG steps. The typical lateral dimensions of these islands were of the order of a few hundred square nanometers, having thickness of up to five monolayers. We modified the shapes and positions of these islands by the STM tip, using a small (less than 1 V) bias voltage.

Probing confinement resonances by photoionizing Xe inside a C60+ molecular cage

Double photoionization accompanied by loss of n C atoms (n=0, 2, 4, 6) was investigated by merging beams of Xe@C60+ ions and synchrotron radiation and measuring the yields of product ions. The giant 4d dipole resonance of the caged Xe atom has a prominent signature in the cross section for these product channels, which together account for 6.2 ± 1.4 of the total Xe 4d oscillator strength of 10. Compared to that for a free Xe atom, the oscillator strength is redistributed in photon energy due to multipath interference of outgoing Xe 4d photoelectron waves that may be transmitted or reflected by the spherical C60+ molecular cage, yielding so-called confinement resonances. The data are compared with an earlier measurement and with theoretical predictions for this single-molecule photoelectron interferometer system. Relativistic R-matrix calculations for the Xe atom in a spherical potential shell representing the fullerene cage show the sensitivity of the interference pattern to the molecular geometry. © 2013 American Physical Society.

Monte Carlo studies of phase transitions and adsorption : application to n-6 Lennard-Jones, C60 and zeolite systems

The solid-fluid transition properties of the n - 6 Lennard-Jones system are studied by means of extensive free energy calculations. Different values of the parameter n which regulates the steepness of the short-range repulsive interaction are investigated. Furthermore, the free energies of the n < 12 systems are calculated using the n = 12 system as a reference. The method relies on a generalization of the multiple histogram method that combines independent canonical ensemble simulations performed with different Hamiltonians and computes the free energy difference between them. The phase behavior of the fullerene C60 solid is studied by performing NPT simulations using atomistic models which treat each carbon in the molecule as a separate interaction site with additional bond charges. In particular, the transition from an orientationally frozen phase at low temperatures to one where the molecules are freely rotating at higher temperatures is studied as a function of applied pressure. The adsorption of molecular hydrogen in the zeolite NaA is investigated by means of grand-canonical Monte Carlo, in a wide range of temperatures and imposed gas pressures, and results are compared with available experimental data. A potential model is used that comprises three main interactions: van der Waals, Coulomb and induced polarization by the permanent electric field in the zeolite.