Superposition of quantum and classical rotational motions in Sc2C2@C84 fullerite.

The superposition of the quantum rotational motion (tunneling) of the encapsulated Sc(2)C(2) complex with the classical rotational motion of the surrounding C(84) molecule in a powder crystal of Sc(2)C(2)@C(84) fullerite is investigated by theory. Since the quantum rotor is dragged along by the C(84) molecule, any detection method which couples to the quantum rotor (in casu the C(2) bond of the Sc(2)C(2) complex) also probes the thermally excited classical motion (uniaxial rotational diffusion and stochastic meroaxial jumps) of the surrounding fullerene. The dynamic rotation-rotation response functions in frequency space are obtained as convolutions of quantum and classical dynamic correlation functions. The corresponding Raman scattering laws are derived, and the overall shape of the spectra and the width of the resonance lines are studied as functions of temperature. The results of the theory are confronted with experimental low-frequency Raman spectra on powder crystals of Sc(2)C(2)@C(84) [M. Krause et al., Phys. Rev. Lett. 93, 137403 (2004)]. The agreement of theory with experiment is very satisfactory in a broad temperature range.

Magnetic fullerenes inside single-wall carbon nanotubes.

C(59)N magnetic fullerenes were formed inside single-wall carbon nanotubes by vacuum annealing functionalized C(59)N molecules encapsulated inside the tubes. A hindered, anisotropic rotation of C(59)N was deduced from the temperature dependence of the electron spin resonance spectra near room temperature. Shortening of the spin-lattice relaxation time T(1) of C(59)N indicates a reversible charge transfer toward the host nanotubes above approximately 350 K. Bound C(59)N-C(60) heterodimers are formed at lower temperatures when C(60) is coencapsulated with the functionalized C(59)N. In the 10-300 K range, T(1) of the heterodimer shows a relaxation dominated by the conduction electrons on the nanotubes.

NMR evidence for gapped spin excitations in metallic carbon nanotubes.

We report on the spin dynamics of 13C isotope enriched inner walls in double-wall carbon nanotubes using 13C nuclear magnetic resonance. Contrary to expectations, we find that our data set implies that the spin-lattice relaxation time (T1) has the same temperature (T) and magnetic field (H) dependence for most of the inner-wall nanotubes detected by NMR. In the high-temperature regime (T approximately > or = 150 K), we find that the T and H dependence of 1/T1T is consistent with a 1D metallic chain. For T approximately < or = 150 K we find a significant increase in 1/T1T with decreasing T, followed by a sharp drop below approximately = 20 K. The data clearly indicate the formation of a gap in the spin excitation spectrum, where the gap value 2delta approximately = 40 K (congruent to 3.7 meV) is H independent.

Isotope engineering of carbon nanotube systems.

The synthesis of a unique isotope engineered system, double-wall carbon nanotubes with natural carbon outer and highly 13C enriched inner walls, is reported from isotope enriched fullerenes encapsulated in single-wall carbon nanotubes (SWCNTs). The material allows the observation of the D line of the highly defect-free inner tubes that can be related to a curvature induced enhancement of the electron-phonon coupling. Ab initio calculations explain the inhomogeneous broadening of inner tube Raman modes due to the distribution of different isotopes. Nuclear magnetic resonance shows a significant contrast of the isotope enriched inner SWCNTs compared to other carbon phases and provides a macroscopic measure of the inner tube mass content. The high curvature of the small diameter inner tubes manifests in an increased distribution of the chemical shift tensor components.

Determination of the diameter distribution of single-wall carbon nanotubes from the Raman G-band using an artificial neural network.

A novel, artificial neural network-based method is now available for obtaining the mean diameter of single wall carbon nanotube (SWCNT) samples from the diameter dispersive features of their Raman G-band. The method is demonstrated here for six different diameter SWCNT samples and 14 different excitation wavelengths. With an adequately large pool of standard nanotube samples, the suggested method is a useful complementary technique for SWCNT diameter analysis as it is capable of rapid diameter evaluation without prior knowledge of the relevant phonon dispersion relations.

Reversible hole engineering for single-wall carbon nanotubes.

Experimental results are provided for reversible generation of holes on single-wall carbon nanotubes and their closing by temperature treatment. The generation of the holes was analyzed by checking the amount of C60 fullerenes that can be filled into the tubes and subsequently transformed to an inner-shell tube. The concentration of the latter was determined from the Raman response of the radial breathing mode. The tube opening process was performed by exposure of the tubes to air at elevated temperatures. This process was found to be independent from the tube diameters. In contrast, the tube closing process was found to depend strongly of the tube diameter. For large diameter tubes (d = 1.8 nm) the activation energy was 1.7 eV whereas for the small diameter tubes this energy was only 0.33 eV. Optimum conditions for tube closing were found to be one hour at 800 degrees C or 10 minutes at 1000 degrees C. From the almost identical Raman spectra for the tubes before and after engineering, a predominant generation of the holes at the tube ends is concluded.

Fullerene quantum gyroscope.

We report the observation of quantized rotational states of a diatomic C2 unit in solid endohedral fullerene C(2)Sc(2)@C(84). The rotational transitions induce a periodic line pattern in the low energy Raman spectrum. The rotational constant B and the C-C distance were found to be 1.73 cm(-1) and 0.127 nm, respectively. Density functional calculations revealed an intrinsic rotational barrier of the order of only a few meV for the C2 unit. The Schrödinger equation involving the potential barrier was solved and the Raman tensor matrix elements were calculated, yielding good quantitative agreement with the experiment. To our best knowledge this is the first intrinsic rotational spectrum of a diatomic plane molecular rotor.

Multipole induced splitting of metal-cage vibrations in crystalline endohedral D2d-M2@C84 dimetallofullerenes.

Metal-carbon cage vibrations of crystalline endohedral D2d-M2@C84 (M=Sc,Y,Dy) dimetallofullerenes were analyzed by temperature dependent Raman scattering and a dynamical force field model. Three groups of metal-carbon cage modes were found at energies of 35-200 cm(-1) and assigned to metal-cage stretching and deformation vibrations. They exhibit a textbook example for the splitting of molecular vibrations in a crystal field. Induced dipole-dipole and quadrupole-quadrupole interactions account quantitatively for the observed mode splitting. Based on the metal-cage vibrational structure it is demonstrated that D2d-Y2@C84 dimetallofullerene retains a monoclinic crystal structure up to 550 K and undergoes a transition from a disordered to an ordered orientational state at a temperature of approximately 150 K.

Unusual high degree of unperturbed environment in the interior of single-wall carbon nanotubes.

Double wall carbon nanotubes were prepared by vacuum annealing of single wall carbon nanotubes filled with C60. Strong evidence is provided for a highly defect free and unperturbed environment in the interior of the tubes. This is concluded from unusual narrow Raman lines for the radial breathing mode of the inner tubes. Lorentzian linewidths scale down to 0.35 cm(-1) which is almost 10 times smaller than linewidths reported so far for this mode. A splitting is observed for the majority of the Raman lines. It is considered to originate from tube-tube interaction between one inner tube and several different outer tubes. The highest RBM frequency detected is 484 cm(-1) corresponding to a tube diameter of only 0.50 nm. Labeling of the Raman lines with the folding vector is provided for all inner tubes. This labeling is supported by density functional calculations.

Origin of the fine structure of the Raman D band in single-wall carbon nanotubes.

Experiments show that the D bands of bundles of single wall carbon nanotubes have a fine structure, apparently consisting of more than one subband. Using the double resonance theory, we calculate for the first time the D band for a sample of a given diameter distribution for seven different laser excitation energies in a wide range. In addition, a detailed theoretical explanation for the fine structure of the D band is provided. The calculated results agree well with experiments and show that the main factors in determining the fine structure are an enhanced trigonal warping of the phonon dispersion, the presence of a diameter distribution in the sample, and--most importantly--the resonance from the Van Hove singularities.

Diameter selective charge transfer in p- and n-doped single wall carbon nanotubes synthesized by the HiPCO method.

The unusually broad diameter distribution of single wall carbon nanotubes (SWCNTs) in a HiPCO derived sample made it possible to observe for the first time a selective loss of Raman resonances corresponding to large diameter tubes upon both p- (FeCl3) and n-type (K) doping.

Phonon softening in metallic nanotubes by a Peierls-like mechanism.

The radial dependency of the vibrational frequencies of single-wall carbon nanotubes in the G band (1500-1600 cm(-1)) is studied by density functional theory. In metallic nanotubes, a mode with A1 symmetry is found to be significantly softer than the corresponding mode in insulating tubes or graphite. The mechanism that leads to the mode softening is explored. It is reminiscent of the driving force inducing Peierls distortions. At ambient temperature, the energy gained by opening the gap is, however, not sufficient for a static lattice distortion. Instead the corresponding vibrational frequency is lowered.

Topochemical polymerization of C70 controlled by monomer crystal packing.

Polymeric forms of C60 are now well known, but numerous attempts to obtain C70 in a polymeric state have yielded only dimers. Polymeric C70 has now been synthesized by treatment of hexagonally packed C70 single crystals under moderate hydrostatic pressure (2 gigapascals) at elevated temperature (300 degrees C), which confirms predictions from our modeling of polymeric structures of C70. Single-crystal x-ray diffraction shows that the molecules are bridged into polymeric zigzag chains that extend along the c axis of the parent structure. Solid-state nuclear magnetic resonance and Raman data provide evidence for covalent chemical bonding between the C70 cages.

Metallic polymers of C(60) inside single-walled carbon nanotubes.

Doping induced polymerization of C(60) inside single-walled carbon nanotubes is reported using Raman spectroscopy and resistivity measurements as a probe. The resistivity changes from semiconducting for the undoped system to metallic for the doped system. For full intercalation, we observe a chemical reaction inside the nanotubes which leads to a one-dimensional polymeric C(60)(-6) chain which has metallic character. The resonance and the oscillations of the radial breathing mode are lost suggesting an up-shift of the Fermi level to beyond the third Van Hove singularity in the semiconducting tubes. The linewidth of the radial breathing mode now represents directly the Gaussian distribution of tube diameters.

Periodic resonance excitation and intertube interaction from quasicontinuous distributed helicities in single-wall carbon nanotubes

Photoselective resonance Raman scattering from laser ablation grown single-wall carbon nanotubes is demonstrated to be consistent with a response from tubes with all geometrically allowed helicities. This information is drawn from an analysis of the resonance scattering by combining ab initio calculations for the mode frequencies with evaluations of the resonance cross sections for isolated tubes. The resonance excitation was found to exhibit an oscillatory behavior. To match the experiments and the calculations, the frequencies obtained from the latter must be up-shifted by 8.5% on the average. This stiffening is ascribed to the tube-tube interaction in the carbon nanotube bundles.