Infrared spectroscopic studies on unoriented single-walled carbon nanotube films under hydrostatic pressure

The electronic properties of as-prepared and purified unoriented single-walled carbon nanotube films were studied by transmission measurements over a broad frequency range (far-infrared up to visible) as a function of temperature (15 K - 295 K) and external pressure (up to 8 GPa). Both the as-prepared and the purified SWCNT films exhibit nearly temperature-independent properties. With increasing pressure the low-energy absorbance decreases suggesting an increasing carrier localization due to pressure-induced deformations. The energy of the optical transitions in the SWCNTs decreases with increasing pressure, which can be attributed to pressure-induced hybridization and symmetry-breaking effects. We find an anomaly in the pressure-induced shift of the optical transitions at $\sim$2 GPa due to a structural phase transition.Comment: 13 pages, 15 figure

Wide-range optical studies on various single-walled carbon nanotubes: the origin of the low-energy gap

We present wide-range (3 meV - 6 eV) optical studies on freestanding transparent carbon nanotube films, made from nanotubes with different diameter distributions. In the far-infrared region, we found a low-energy gap in all samples investigated. By a detailed analysis we determined the average diameters of both the semiconducting and metallic species from the near infrared/visible features of the spectra. Having thus established the dependence of the gap value on the mean diameter, we find that the frequency of the low energy gap is increasing with increasing curvature. Our results strongly support the explanation of the low-frequency feature as arising from a curvature-induced gap instead of effective medium effects. Comparing our results with other theoretical and experimental low-energy gap values, we find that optical measurements yield a systematically lower gap than tunneling spectroscopy and DFT calculations, the difference increasing with decreasing diameter. This difference can be assigned to electron-hole interactions.Comment: 9 pages, 8 figures, to be published in Physical Review B, supplemental material attached v2: Figures 1, 7 and 8 replaced, minor changes to text; v3: Figures 3, 4 and 5 replaced, minor changes to tex

Pressure-induced transition from the dynamic to static Jahn-Teller effect in (Ph4_{4}P)2_{2}IC60_{60}

High-pressure infrared transmission measurements on \PhC60 were performed up to 9 GPa over a broad frequency range (200 - 20000 cm$^{-1}$) to monitor the vibrational and electronic/vibronic excitations under pressure. The four fundamental T$_{1u}$ modes of \C60a\ are split into doublets already at the lowest applied pressure and harden with increasing pressure. Several cation modes and fullerene-related modes split into doublets at around 2 GPa, the most prominent one being the G$_{1u}$ mode. The splitting of the vibrational modes can be attributed to the transition from the dynamic to static Jahn-Teller effect, caused by steric crowding at high pressure. Four absorption bands are observed in the NIR-VIS frequency range. They are discussed in terms of transitions between LUMO electronic states in \C60a, which are split because of the Jahn-Teller distortion and can be coupled with vibrational modes. Various distortions and the corresponding symmetry lowering are discussed. The observed redshift of the absorption bands indicates that the splitting of the LUMO electronic states is reduced upon pressure application.Comment: 10 pages, 17 figure

Study of charge dynamics in transparent single-walled carbon nanotube films

We report the transmission over a wide frequency range (far infrared - visible) of pristine and hole-doped, free-standing carbon nanotube films at temperatures between 50 K and 300 K. Optical constants are estimated by Kramers-Kronig analysis of transmittance. We see evidence in the far infrared for a gap below 10 meV. Hole doping causes a shift of spectral weight from the first interband transition into the far infrared. Temperature dependence in both the doped and undoped samples is restricted to the far-infrared region.Comment: 6 pages, 4 figures, submitted to Phys. Rev. B v3: Fig. 2 replaced, changes in caption of Table II, minor changes in tex

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]

Giant microwave absorption in fine powders of superconductors

Enhanced microwave absorption, larger than that in the normal state, is observed in fine grains of type-II superconductors (MgB$_2$ and K$_3$C$_{60}$) for magnetic fields as small as a few $\%$ of the upper critical field. The effect is predicted by the theory of vortex motion in type-II superconductors, however its direct observation has been elusive due to skin-depth limitations; conventional microwave absorption studies employ larger samples where the microwave magnetic field exclusion significantly lowers the absorption. We show that the enhancement is observable in grains smaller than the penetration depth. A quantitative analysis on K$_3$C$_{60}$ in the framework of the Coffey--Clem (CC) theory explains well the temperature dependence of the microwave absorption and also allows to determine the vortex pinning force constant

Static and dynamic Jahn-Teller effect in the alkali metal fulleride salts A4C60 (A = K, Rb, Cs)

We report the temperature dependent mid- and near-infrared spectra of K4C60, Rb4C60 and Cs4C60. The splitting of the vibrational and electronic transitions indicates a molecular symmetry change of C604- which brings the fulleride anion from D2h to either a D3d or a D5d distortion. In contrast to Cs4C60, low temperature neutron diffraction measurements did not reveal a structural phase transition in either K4C60 and Rb4C60. This proves that the molecular transition is driven by the molecular Jahn-Teller effect, which overrides the distorting potential field of the surrounding cations at high temperature. In K4C60 and Rb4C60 we suggest a transition from a static to a dynamic Jahn-Teller state without changing the average structure. We studied the librations of these two fullerides by temperature dependent inelastic neutron scattering and conclude that both pseudorotation and jump reorientation are present in the dynamic Jahn-Teller state.Comment: 13 pages, 10 figures, to be published in Phys. Rev.

Direction-dependent secondary bonds and their stepwise melting in a uracil-based molecular crystal studied by infrared spectroscopy and theoretical modeling

Three types of supramolecular interactions are identified in the three crystallographic directions in crystals of 1,4-bis[(1-hexylurac-6-yl)ethynyl]benzene, a uracil-based molecule with a linear backbone. These three interactions, characterized by their strongest component, are: intermolecular double H-bonds along the molecular axis, London dispersion interaction of hexyl chains connecting these linear assemblies, and $\pi$--$\pi$ stacking of the aromatic rings perpendicular to the molecular planes. On heating, two transitions happen, disordering of hexyl chains at 473 K, followed by H-bond melting at 534 K. The nature of the bonds and transitions was established by matrix-isolation and temperature-dependent infrared spectroscopy and supported by theoretical computations

Structure and properties of the stable two-dimensional conducting polymer Mg5C60

We present a study on the structural, spectroscopic, conducting, and magnetic properties of Mg5C60, which is a two-dimensional (2D) fulleride polymer. The polymer phase is stable up to the exceptionally high temperature of 823 K. The infrared and Raman studies suggest the formation of single bonds between the fulleride ions and possibly Mg-C-60 covalent bonds. Mg5C60 is a metal at ambient temperature, as shown by electron spin resonance and microwave conductivity measurements. The smooth transition from a metallic to a paramagnetic insulator state below 200 K is attributed to Anderson localization driven by structural disorder