Evidence of 1D behaviour of He4^4 confined within carbon-nanotube bundles

We present the first low-temperature thermodynamic investigation of the controlled physisorption of He$^{4}$ gas in carbon single-wall nanotube (SWNT) samples. The vibrational specific heat measured between 100 mK and 6 K demonstrates an extreme sensitivity to outgassing conditions. For bundles with a few number of NTs the extra contribution to the specific heat, C$_{ads}$, originating from adsorbed He$^{4}$ at very low density displays 1D behavior, typical for He atoms localized within linear channels as grooves and interstitials, for the first time evidenced. For larger bundles, C$_{ads}$ recovers the 2D behaviour akin to the case of He$^{4}$ films on planar substrates (grafoil).Comment: 4 pages, 3 figures, submitted to Phys. Rev. Let

Raman spectroscopy of iodine-doped double-walled carbon nanotubes

We present a Raman spectroscopy study of iodine-intercalated (p-type-doped) double-walled carbon nanotubes. Double-walled carbon nanotubes (DWCNTs) are synthesized by catalytic chemical vapor deposition and characterized by Raman spectroscopy. The assignment of the radial breathing modes and the tangential modes of pristine DWCNTs is done in the framework of the bond polarization theory, using the spectral moment method. The changes in the Raman spectrum upon iodine doping are analyzed. Poly-iodine anions are identi- fied, and the Raman spectra reveal that the charge transfer between iodine and DWCNTs only involves the outer tubes

Low frequency excitations of C60 chains inserted inside single-walled carbon nanotubes

The low frequency excitations of C60 chains inserted inside single-walled carbon nanotubes (SWNTs) have been studied by inelastic neutron scattering (INS) on a high quality sample of peapods. The comparison of the neutron-derived generalized phonon density of states (GDOS) of the peapods sample with that of a raw SWNTs allows the vibrational properties of the C60 chains encapsulated in the hollow core of the SWNTs to be probed. Lattice dynamical models are used to calculate the GDOS of chains of monomers, dimers and polymers inserted into SWNTs, which are compared to the experimental data. The presence of strong interactions between C60 cages inside the nanotube is clearly demonstrated by an excess of mode density in the frequency range around 10 meV. However, the presence of a quasi-elastic signal indicates that some of the C60\'s undergo rotational motion. This suggests that peapods are made from a mixture of C60 monomers and C60 n-mer (dimer, trimer ... polymer) structures

Microscopic theory of glassy dynamics and glass transition for molecular crystals

We derive a microscopic equation of motion for the dynamical orientational correlators of molecular crystals. Our approach is based upon mode coupling theory. Compared to liquids we find four main differences: (i) the memory kernel contains Umklapp processes, (ii) besides the static two-molecule orientational correlators one also needs the static one-molecule orientational density as an input, where the latter is nontrivial, (iii) the static orientational current density correlator does contribute an anisotropic, inertia-independent part to the memory kernel, (iv) if the molecules are assumed to be fixed on a rigid lattice, the tensorial orientational correlators and the memory kernel have vanishing l,l'=0 components. The resulting mode coupling equations are solved for hard ellipsoids of revolution on a rigid sc-lattice. Using the static orientational correlators from Percus-Yevick theory we find an ideal glass transition generated due to precursors of orientational order which depend on X and p, the aspect ratio and packing fraction of the ellipsoids. The glass formation of oblate ellipsoids is enhanced compared to that for prolate ones. For oblate ellipsoids with X <~ 0.7 and prolate ellipsoids with X >~ 4, the critical diagonal nonergodicity parameters in reciprocal space exhibit more or less sharp maxima at the zone center with very small values elsewhere, while for prolate ellipsoids with 2 <~ X <~ 2.5 we have maxima at the zone edge. The off-diagonal nonergodicity parameters are not restricted to positive values and show similar behavior. For 0.7 <~ X <~ 2, no glass transition is found. In the glass phase, the nonergodicity parameters show a pronounced q-dependence.Comment: 17 pages, 12 figures, accepted at Phys. Rev. E. v4 is almost identical to the final paper version. It includes, compared to former versions v2/v3, no new physical content, but only some corrected formulas in the appendices and corrected typos in text. In comparison to version v1, in v2-v4 some new results have been included and text has been change

Accurate determination of the chiral indices of individual carbon nanotubes by combining electron diffraction and Resonant Raman spectroscopy

The experimental approach combining high resolution transmission electron microscopy (HRTEM), electron diffraction (ED) and resonant Raman spectroscopy (RRS) on the same free-standing individual carbon nanotubes (CNT) is the most efficient method to determine unambiguously the intrinsic features of the Raman-active phonons. In this paper, we review the main results obtained by the approach regarding the intrinsic features of the phonons of single-walled (SWNT) and double-walled carbon nanotubes (DWNT). First, we detail the different methods to identify the structure of SWNTs and DWNTs from the analysis of their electron diffraction patterns (EDP). In the following, we remind the principal features of the Raman response of SWNTs, unambiguously index-identified by ED. A special attention is devoted to the effect of the inter-layer interaction on the frequencies of the Raman-active phonons in index-identified DWNTs. The information obtained on index-identified SWNT and DWNT allows us to propose Raman criteria, which help identifying CNT when the ED fails to propose a single assignment. The efficiency of the Raman criteria as the complement to the ED information for the index-assignment of a few SWNTs and DWNTs is shown. The same approach to index-assign a triple-walled carbon nanotube (TWNT), by combining ED and RRS information, is reported

Insights into the Second Law of Thermodynamics from Anisotropic Gas-Surface Interactions

Thermodynamic implications of anisotropic gas-surface interactions in a closed molecular flow cavity are examined. Anisotropy at the microscopic scale, such as might be caused by reduced-dimensionality surfaces, is shown to lead to reversibility at the macroscopic scale. The possibility of a self-sustaining nonequilibrium stationary state induced by surface anisotropy is demonstrated that simultaneously satisfies flux balance, conservation of momentum, and conservation of energy. Conversely, it is also shown that the second law of thermodynamics prohibits anisotropic gas-surface interactions in "equilibrium", even for reduced dimensionality surfaces. This is particularly startling because reduced dimensionality surfaces are known to exhibit a plethora of anisotropic properties. That gas-surface interactions would be excluded from these anisotropic properties is completely counterintuitive from a causality perspective. These results provide intriguing insights into the second law of thermodynamics and its relation to gas-surface interaction physics.Comment: 28 pages, 11 figure

Photoluminescence from an individual double-walled carbon nanotube

We report direct and unambiguous evidence of the existence of inner semiconducting tube (ISCT) photoluminescence (PL) from measurements performed on four individual freestanding index-identified double-walled carbon nanotubes (DWNTs). Based on thorough Rayleigh scattering, Raman scattering, and PL experiments, we are able to demonstrate that the ISCT PL is observed with a quantum yield estimated to be a few 10-6 independent of the semiconducting or metallic nature of the outer tube. This result is mainly attributed to ultrafast exciton transfer from the inner to outer tube. Furthermore, by carrying out PL excitation experiments on the (14, 1)@(15, 12) DWNT, we show that the ISCT PL can be detected through the optical excitation of the outer tube, indicating that the exciton transfer can also occur in the opposite way

Far-infrared study of the Jahn-Teller distorted C60 monoanion in C60 tetraphenylphosphoniumiodide

We report high-resolution far-infrared transmission measurements on C(60)-tetraphenylphosphoniumiodide as a function of temperature. In the spectral region investigated (20-650 cm(-1)), we assign intramolecular modes of the C(60) monoanion and identify low-frequency combination modes. The well-known F(1u)(1) and F(1u)(2) modes are split into doublers at room temperature, indicating a D(5d) or D(3d) distorted ball. This result is consistent with a dynamic Jahn-Teller effect in the strong-coupling limit or with a static distortion stabilized by low-symmetry perturbations. The appearance of silent odd modes is in keeping with symmetry reduction of the hall, while activation of even modes is attributed to interband electron-phonon coupling and orientational disorder in the fulleride salt. Temperature dependences reveal a weak transition in the region 125-150 K in both C(60)(-) and counterion modes, indicating a bulk, rather than solely molecular, effect. Anomalous softening (with decreasing temperature) in several modes may correlate with the radial character of those vibrations. [S0163-1829(98)03245-7]

Interlayer Dependence of G-Modes in Semiconducting Double-Walled Carbon Nanotubes

A double-walled carbon nanotube (DWNT), a coaxial composite of two single walled carbon nanotubes (SWNT), provides a unique model to study interactions between thetwo constituent SWNTs. Combining high resolution transmission electron microscopy (HRTEM), electron diffraction (ED), and resonant Raman scattering (RRS) experiments on the same individual suspended DWNT is the ultimate way to relate unambiguously its atomicstructure, defined by the chiral indices of the coaxial outer/inner SWNTs, and its Raman-active vibration modes. This approach is used to investigate the intertube distance dependence of theG-modes of individual index-identified DWNTs composed of two semiconducting SWNTs.We state the main features of the dependence of the G-mode frequencies on the distance between the inner and outer layers: (i) When the interlayer distance is larger than the nominal van der Waals distance (close to 0.34 nm), a downshift of the inner-layer G-modes with respectto the G-modes in the equivalent SWNTs is measured. (ii) The amplitude of the downshiftdepends on the interlayer distance, or in other words, on the negative pressure felt by the innerlayer in DWNT. (iii) No shift is observed for an intertube distance close to 0.34 nm

Charge transfer in conjugated oligomers encapsulated into carbon nanotubes

This study deals with a hybrid system consisting in quaterthiophene derivative encapsulated inside single-walled and multi-walled carbon nanotubes. Investigations of the encapsulation step are performed by transmission electron microscopy. Raman spectroscopy data point out different behaviors depending on the laser excitation energy with respect to the optical absorption of quaterthiophene. At low excitation energy (far from the oligomer resonance window) there is no significant modification of the Raman spectra before and after encapsulation. By contrast, at high excitation energy (close to the oligomer resonance window), Raman spectra exhibit a G-band shift together with an important RBM intensity loss, suggesting a significant charge transfer between the inserted molecule and the host nanotubes. Those results suggest a photo induced process leading to a significant charge transfer.Peer reviewe