Synthesis and Raman scattering study of double-walled carbon nanotube peapods

Double-walled carbon nanotubes (DWNTs) encapsulating C₆₀ fullerenes were successfully synthesized by gas phase diffusion method. The obtained peapods were examined using high-resolution transmission electron microscopy (HRTEM). The HRTEM images indicate that the ordered packing phases of fullerene molecules inside are sensitively related to the inner-tube radius of DWNTs. Also, Raman measurements were carried out for the first time to characterize DWNTs peapods. There are obvious differences between the Raman spectrum of DWNTs peapods and that of SWNTs peapods. The intensities of resonances from C₆₀ in the former are much stronger than those in the latter. In addition, changes of tangential mode (TM) and radial breathing mode (RBM) of DWNTs after C₆₀ doping were observed. The possible reasons are discussed in the text.     

Site selectivities of alkali ions in CsRb2C60 and Cs2RbC60 superconductors

The temperature-dependent site selectivities of Cs and Rb ions in CsRb₂C₆₀ and Cs₂RbC₆₀ superconductors are computed using the free energy obtained from the configuration entropy and the total energy calculated using the ab initio pseudopotential density-functional theory. It is found that in CsRb₂C₆₀ the smaller Rb ions can occupy a considerable number of large octahedral interstitial sites at high temperatures, however, the transition to random occupation never takes place. For Cs₂RbC₆₀ the Cs occupancy of the large octahedral interstitial sites is almost always 100%, and, interestingly, the two tetrahedral interstitial sites are randomly occupied by Cs and Rb ions even at very low temperatures.     

On the encapsulation of azafullerenes inside the single-walled carbon nanotubes: Density-functional theory based treatments

We theoretically studied the encapsulation of azafullerene (C₅₉N) inside the single-walled carbon nanotubes (SWCNTs) from the first-principles. Adsorption energy is calculated, and the azafullerene affinities for the typical semiconducting and metallic nanotubes are investigated and compared with those of pure C₆₀ fullerene. It has been found that the azafullerene as well as the fullerene affinity for the semiconducting nanotubes is stronger than that for the metallic ones, and the energy values and binding distances are typical for the physisorption. Our first-principles results indicate that the interaction between SWCNTs and azafullerenes is comparable with the nanotubes-C₆₀ system. The charge analysis shows, however, that the charges have been transferred from the cage to the tube in the azafullerene peapods, while in the fullerene peapods the charges were found to be transferred from the tube to the fullerene nanocage. Furthermore, it was found that the interaction between the considered fullerenes and host nanotubes strongly depends on the tube diameters.     

The electron transport properties of photo- and electron-beam-irradiated C60 films

The electron transport properties of photo- and electron-beam-induced C₆₀ polymers, in which the former is a dumbbell-type two-dimensional (2D) polymer and the latter is a new polyhedral structured (peanut-shaped) carbon nanomaterial, have been investigated. Using a four-probe measurement, we found that the 2D photopolymer and the peanut-shaped polymer exhibit semiconducting and metallic characters in air at room temperature, respectively. In order to elucidate the origin of these electron transport properties, we have performed density-functional calculations of the dumbbell-shaped and peanut-shaped C₁₂₀ dimers that can be regarded as a basic unit of each polymer. It was found that the HOMO consisting of π-electrons orbital, which is related to the electron transport property, has a node on the [2+2] cyclo-bond for the dumbbell-shaped dimer, while that the HOMO has no node on the cross-linkage and spreads over the peanut-shaped dimer.     

Sm富勒烯的价带光电子能谱

用紫外光电子能谱和同步辐射光电子能谱研究了Sm掺杂C₆₀薄膜的价带电子结构.Sm的价电子大部分转移给C₆₀，化学键以离子性为主.对于任何化学配比都没有观察到费米边，所以Sm富勒烯超导相在室温下为半导体性质.获得了很接近单相Sm_2.75C₆₀的样品在费米能级附近的电子态密度分布.固溶相的光电子发射与Sm_2.75C₆₀有明显区别.Sm_xC_{60关键词： 60}的Sm填隙化合物')" href="#">C₆₀的Sm填隙化合物 价带光电子能谱 电子结构     

Modulation of the work function of fullerenes C60 and C70 by alkali-metal adsorption: A theoretical study

The impact of alkali-metal (Li/Na/Cs) adsorption on work function of fullerenes C₆₀ and C₇₀ was investigated by first-principles calculations. After adsorption, the work functions of fullerenes C₆₀ and C₇₀ decrease distinctly and vary linearly with the electronegativity of the alkali metal elements, and the positions where the alkali atoms are adsorbed considerably influence the work functions. On the contrary, a vacancy defect elevates the work functions of the fullerenes C₆₀ and C₇₀. The variation in the work functions rests with variation in Fermi level (which are attributed to charge transfer) and variation in vacuum levels (which are attributed to the induced dipole moments). Moreover, alkali-metal adsorption can also improve the electric conductivity of a fullerene mixture of C₆₀ and C₇₀.     

Structures and energetics of carbon bridged C 60 clusters

The structures and energetics of carbon bridged C₆₀ clusters (C ₆₀ ) _n C_m have been studied by simulated annealing technique within the tight-binding molecular-dynamics. The “sp² addition” ball-and-chain dimers exhibit odd-even alternations over the number of chain atoms, with the dimers containing even chain atoms more stable against dissociation than their immediate neighbors containing odd chain atoms. In addition to the usual “sp² addition” dimers, a pentagon-linked C₁₂₁ isomer and a hexagon-linked C₁₂₂ isomer are also found to be stable. Based on our tight-binding calculations, trimers and larger clusters can be simply regarded as being made up of independent or weakly interacting dimers, if the C-C₆₀ joints on a single cage are not too close to each other. Large C₆₀ clusters connected by chains each containing only one or two carbon atoms have similar stability to that of constituent dimers, indicating the possibility to form stable C₆₀-carbon polymers. Received 17 January 2001 and Received in final form 26 February 2001     

Thermoelectric power factor of RuSr2GdCu2O8

The influence of thermal treatment between 1273 and 1333?K in an oxygen atmosphere on the perovskite system RuSr₂GdCu₂O₈ was studied by X-ray diffraction (XRD), scanning electron microscopy, electrical resistivity and Seebeck coefficient measurements. The XRD patterns revealed that the phase purity depends on the sintering process. The samples were found to exhibit very small crystallite sizes in the nanometer range. The electrical resistivity was found to be strongly correlated with the heat treatment. The temperature dependence of electrical resistivity for one sample revealed semiconducting behavior, whereas the others exhibit metallic behavior. All the investigated samples exhibit a positive thermoelectric power, indicating the predominance of positive charge carriers. It was found that the power factor reaches a maximum value of 0.4?×?10^?4?W?m^?1?K^?2 at 300?K.     

Photo-and pressure-induced transformations in the linear orthorhombic polymer of C<Subscript>60</Subscript>

Stability of the linear orthorhombic polymer of C₆₀ under pressure and laser irradiation is studied by Raman scattering and X-ray diffraction measurements. The Raman spectrum at ambient pressure remains unchanged, in the time scale of the experiment, up to an intensity of 3200 W/cm² of the 514.5 nm line of an Ar⁺ laser, but irreversible changes are observed at higher intensities. The Raman spectra recorded at increased pressure show similar irreversible changes even at the laser intensity as low as 470 W/cm². The X-ray diffraction and Raman measurements of the pressure-treated samples, performed after pressure release, show that the nonirradiated material does not exhibit any changes in the crystal structure and phonon spectra. This behavior indicates a pressure-enhanced photo-induced transformation to a new polymeric phase characterized by a Raman spectrum that differs from those of the other known polymeric phases of C₆₀. The Raman spectra of the phototransformed linear orthorhombic polymer of C₆₀ were measured at a pressure of up to 29 GPa. The pressure dependence of the Raman mode frequencies show singularities near 4 GPa and 15 GPa, respectively, related to a reversible phase transition and an irreversible transformation to a metastable disordered phase. The diffuse Raman spectrum of the disordered phase does not exhibit substantial changes with an increase in pressure up to 29 GPa. The high-pressure phase transforms to a mixture of pristine and dimerized C₆₀, after pressure release and exposure to ambient conditions for 30 h. The text was submitted by the authors in English.     

13C MAS NMR investigations of alkali doped C60

Results of¹³C MAS NMR measurements of the Rb _x C₆₀ system (x=2.75, 3, 4, 6) and the A₆C₆₀ compounds (A=K, Rb, Cs) are presented. Special attention was paid to sample preparation in order to suppress effects of impurities and lattice defects due to imperfect C₆₀ starting material. The¹³C MAS NMR measurements of the Rb _x C₆₀ system demonstrate the usefulness of this method to reveal valuable information about its phase diagram. The existence of underdoped Rb₃C₆₀ is proved. Well resolved lines in all investigated A₆C₆₀ compounds confirm the orientational order of the C₆₀ ions. An assignment of the signals to the three magnetically inequivalent carbon atom positions in the crystal structure is proposed.     

High-field electron paramagnetic resonance study of the polymerization in Na2Rb1−x Cs x C60

We report on the study of the magnetic properties of the low-temperature polymer phases in N₂Rb_1?xCs_xC₆₀ at 110 GHz microwave frequency withx varying between 0 and 1. The magnetic and structural properties of the polymer phase strongly depend on the Cs content and its electronic structure progressively becomes quasi-one-dimensional asx is increased. While the electronic properties of the polymeric Na₂RbC₆₀ appear to be close to three-dimensional metal, Na₂Rb_0.3Cs_0.7C₆₀ shows characteristics of quasi-one-dimensional metal where instability in the electronic structure was found as detected by the sudden disappearance of the ESR intensity due to the opening of the gap at the Fermi surface. The observation of an additional resonance line below 15 K, which could be attributed to antiferromagnetic resonance, suggests that the low-temperature polymeric phase in Na₂Rb_0.3Cs_0.7C₆₀ has a well-defined magnetic ground state.     

Magnetic, electrical, and crystallographic properties of thin La1−x SrxMnO3 films

A study is reported of the magnetic, electrical, and crystallographic properties of La_1−x Sr_xMnO₃ (0.15⩽x⩽0.23) epitaxial films grown on single-crystal substrates of (001)ZrO₂(Y₂O₃) having the fluorite structure and (001)LaAlO₃ having the perovskite structure. It was found that films with close compositions for x=0.15 and 0.16, grown on different substrates, have different properties, namely, the film on a fluorite substrate is semiconducting and has a coercive strength 30 times that of the film on a perovskite substrate; the temperature dependence of electrical resistance of the latter film has a maximum around the Curie point T _C and follows metallic behavior for T<T _C. These differences are explained as due to different structures of the films. The x=0.23 film on the perovskite substrate has been found to exhibit a combination of giant magnetoresistance at room temperature with a resistance of ≈300 Ω which is useful for applications. The maxima in resistance and absolute value of negative magnetoresistance are accounted for by the existence of two-phase magnetic states in these films. Fiz. Tverd. Tela (St. Petersburg) 40, 290–294 (February 1998)     

7Li and 133Cs NMR parameters in C6Li and C8Cs intercalated oriented graphites

The absolute values of the Knight shift in C₆Li and C₈Cs, prepared from highly oriented pyrolytic graphite, are found to be very different. Comparison to the corresponding values of Li and Cs metal, however, shows that the Knight shift reductions are similar. Nevertheless, the origins of these reductions are different in accordance with the different electronic structures of these compounds.     

Rb掺杂C60单晶的相衍变和电子态

在C₆₀单晶超高真空解理面上制备C₆₀的Rb填隙化合物薄膜.用同步辐射光电子能谱研究了相衍变过程.观察到对应于固溶相、Rb₁C₆₀和Rb₃C₆₀的电子态密度分布.当数纳米厚Rb₃C₆₀薄膜在C₆₀单晶（111）解理面形成后，室温条件下进一步沉积Rb至样品表面不产生fcc到bct或bcc结构相变.C_{60 关键词： 4}C₆₀和Rb₅C₆₀吸附相')" href="#">金属性Rb₄C₆₀和Rb₅C₆₀吸附相 60单晶')" href="#">C₆₀单晶 相衍变 同步辐射光电子能谱     

Adsorption of N@C60 on Si(1 0 0)

The interactions between endohedrally doped N@C₆₀ molecules and the Si(1 0 0) surface have been explored via ab initio total energy calculations. Configurations which have the cage located upon the dimer row bonded to two dimers (r2) and within the dimer trench bonded to four dimers (t4) have been investigated, as these have previously been found to be the most stable for the C₆₀ molecule. We have investigated the differences between the adsorption of the C₆₀ and N@C₆₀ molecules upon the Si(1 0 0) surface and found that there are only minimal differences. Two interesting cases are the r2g and t4d configurations, as they both exhibit differences that are not present in the other configurations. These subtle differences have been explored in-depth. It is shown that the effects on the endohedral nitrogen atom, due to its placement within the fullerene cage, are small. Bader analysis has been used to explore differences between the C₆₀ and N@C₆₀ molecules.     

Electronic properties of ortho-polymer A1C60 (A = K,Rb) and related phases

1 C₆₀. Its singular structural, magnetic and electrical properties greatly enhanced the study of the AC₆₀ phases (A = Rb, K and \chem{Cs}). We report our continuous wave (cw) ESR results on the structural phase transformations, phase instabilities and the related kinetics of K₁C₆₀. We quantitatively explain the origin of the difference between Rb₁C₆₀ and K₁C₆₀ phase diagrams. The stability of OP-Rb₁C₆₀ together with the narrowness of its homogenous cw-ESR linewidth in the temperature range allow to perform pulsed ESR experiments. Pulsed ESR experiments measure precisely both the electronic spin-spin () and spin-lattice () relaxation times. Above , the equality of and , which are the only contributions to the cw-ESR linewidth, constitutes a convincing evidence of the metallic nature of OP-Rb₁C₆₀. The drastic increase (decrease) of the linewidth () below \valunit{40}{K} is interpreted in terms of an \qut{electronic dimerization}. Received: 12 September 1996/Accepted: 14 November 1996     

Solution‐Based Phototransformation of C60 Nanorods: Towards Improved Electronic Devices

A modified liquid–liquid interface precipitation synthesis of C₆₀ nanorods, effects and opportunities following an in situ photochemical transformation in the liquid state, and an electronic characterization using a field‐effect transistor (FET) geometry are reported. The nanorods feature a high aspect ratio of ≈10³ and a notably small average diameter of 172 nm. Interestingly, it is found that a decreased nanorod diameter appears to correlate with distinctly improved electronic properties, and an average electron mobility of 0.30 cm² V^?1 s^?1, as measured in a FET geometry, is reported for as‐grown nanorods, with the peak value being an impressive 1.0 cm² V^?1 s^?1. A photoexposure using green laser light (λ = 532 nm) is demonstrated to result in the formation of a polymer‐C₆₀ shell encapsulating a monomer‐C₆₀ bulk; such photo‐transformed nanorods exhibit an electron mobility of 4.7 × 10^?3 cm² V^?1 s^?1. It is notable that the utilized FET geometry only probes the polymer‐C₆₀ nanorod surface shell, and that the monomer‐C₆₀ bulk is anticipated to exhibit a higher mobility. Importantly, photoexposed nanorods can be conveniently processed as a stabile dispersion in common hydrophobic solvents, and this finding is attributed to the insoluble character of the polymer‐C₆₀ shell.     

Manifestation of quantum statistics in vibrational dynamics of poly(ethylene) crystals

The temperature dependences of the transverse expansion ?_⊥(T) and the longitudinal contraction ?_‖(T) (with respect to the axes of chain molecules) in large-sized poly(ethylene) (PE) crystal grains (100×60×60 nm) are measured using x-ray diffraction in the temperature range 5–380 K. The temperature dependence of the elongation of the molecular skeleton ?_C(T) is obtained by Raman spectroscopy. It is found that the dependences ?_⊥(T), ?_‖(T), and ?_C(T) exhibit a similar specific nonlinear behavior. Analysis of these dependences indicates that the nonlinearity is associated with the quantum statistics of transverse vibrations. The energies and amplitudes of zero-point (at T=0) transverse (torsional and bending) vibrations and the relevant zero-point components ?_‖(0) and ?_C(0) are estimated. It is revealed that the zero-point components make a considerable contribution to the dynamics of the PE crystal up to the melting temperature (～400 K).     

Splitting of the electronic states near EF in A4C60 compounds (A = alkali metal)

The electronic structure of A₄C6₀ compounds (A=Na, K, Cs) has been studied using electron energy-loss spectroscopy. Both the low energy loss functions and Cls core excitation measurements reveal a strong splitting of the electronic states near the Fermi level in comparison with K₃C₆₀ or K₆C₆₀. This splitting indicates a lowering of the high degeneracy of the C₆₀ molecular orbitals due to a broken symmetry ground state and/or the opening of a correlation gap in these systems.     

[2.2.2]Paracyclophane as a receptor for the cesium cation in the gas phase

By using electrospray ionisation mass spectrometry, it was proven experimentally that the cesium cation (Cs⁺) forms with [2.2.2]paracyclophane (C₂₄H₂₄) the cationic complex [Cs(C₂₄H₂₄)]⁺. Further, applying quantum chemical calculations, the most probable structure of the [Cs(C₂₄H₂₄)]⁺ complex was derived. In the resulting complex with a symmetry very close to C₃, the ‘central’ cation Cs⁺, fully located in the cavity of the parent [2.2.2]paracyclophane ligand, is bound to all three benzene rings of [2.2.2]paracyclophane via cation–π interaction. Finally, the interaction energy, E(int), of the considered cation–π complex [Cs(C₂₄H₂₄)]⁺ was found to be ?73.2 kJ/mol, confirming the formation of this fascinating complex species as well. This means that [2.2.2]paracyclophane can be considered as a receptor for the Cs⁺ cation in the gas phase.