Fullerene (C60 and C70) synthesis by combustion of ethylene and benzene in a flat flame burner was investigated. This method of fullerene synthesis is particularly attractive because of its potential of scale up. Also the ability to change the flame conditions andcontrol the yield of C60 and C70 makes this method versatile. No fullerenes were found in soot samples collected from the ethylene flame. However, fullerenes were formed in a benzene flame with C/O = 0.88 and operated at 40 torr, with cold gas velocity of 25.3 cm/s (273 K) and containing 10% argon. The concentration of fullerenes in this flame was found to depend strongly on the height above the burner surface. It exhibited a strong maxima at about 1.0 cm above the burner height suggesting the presence of both growth and destruction mechanisms.

C60 molecules have been studied at both shock and static high pressures. Under shock compressions C60 fullerenes are stable into the 13-17 GPa pressure range. The onset of a fast (∼0.5 μs) reconstructive transformation to graphite occurs near 17 GPa. The graphite recovered from 27 GPa and about 900 K is relatively well ordered with La = 100 Å. Above 50 GPa a continuous transformationto an amorphous state is observed in recovered specimens. A transparent, metastable carbon phase was recovered from thin films of C60, shocked to 69 GPa and 2200 K and then rapidly quenched to 1000 K. The selected area diffraction patterns indicate thatthe metastable carbon contains an amorphous diamond and n-diamond. Under hydrostatic compressions C60 molecules transform reversibly to a semi-transparent phase in the pressure range of 15-25 GPa with a large pressure hysteresis. The high pressure phaseconsists of interconnected strongly interacting C60 agglomerates, or networksof fullerenes, whose stability continuously increases with increase of pressure. Above 27 GPa the transition becomes irreversible, and the material recovered from high pressureis metastable and diamond-like at ambient conditions. These pressure-induced transitions are explained in terms of nr-electron rehybridization between C60 molecules, which occurs at substantially decreased intermolecular distances.

The dimensionless electron-phonon coupling parameter in alkali metal-doped fullerenes isevaluated in a model whereby the electrons are treated within a tight binding formalism.The phonon mode frequencies and eigenvectors are obtained from a lattice dynamical modelwhich accurately fits all available experimental data on these modes. It is shown that the electrormphonon interaction can account for the relatively high values of the superconducting transition temperatures in alkali-metal fullerenes.

In a series of experiments on solid C60, the low-energy rotational dynamics of the molecules, the higher-energy vibrational spectra, and aspects of disorder in the static structure, have been studied. The nearly spherical shape of the C60 molecule, and the occurrence of an orientational phase transition at Tc=256 K, make the C60 solid an excellent system for investigations of orientational dynamics. Coherent quasi-elastic neutron scattering above Tc is described quantitatively by a rotational diffusion model. Below Tc, inelastic scattering froma soft librational mode is observed between 2 and 3 meV. Models of the strong, temperaturedependent diffuse scattering due to orientational disorder are discussed. Finally, measurements of the density of states for the intramolecular ( E ≥ 33 meV) vibrational modes are also presented.

Raman scattering measurements in alkali—fullerene alloys in ultrathin and thin films provide evidence for variations in electron—phonon coupling. For x — 3similar behavior of Rb3 C60 films of different thickness support substantial electron—phonon induced damping of specific Hg(i) modes derived from intramolecular modes of C60. In 400A thick films a reduction of induced scattering from Raman inactive C60 modes substantiates the importance ofHg(2), but not Hg(3) modes for phonon—mediated superconductivity. In contrast to RbxC60 and KxC60 ultrathin film solid solutions, similar Raman spectra for NaxC60 indicate substantially reduced coupling consistent with the absence of superconductivity in this system.

The phonon spectra of pristine fullerene, superconducting K3C60 and saturation-doped Rb6C60 measured by inelastic neutron scatteringin the energy range 2.5 - 200 meV at low temperatures reveal substantial broadening of five-fold degenerate Hg intramolecular vibrational modes both in the low-energy radial and the high-energy tangential part of the spectrum. This provides strong evidence for a traditional phonon-mediated mechanism of superconductivity in the fullerides but with an electron-phonon coupling strength distributed over a wide range of energies (33-195 meV) as a result of the finite curvature of the fullerene spherical cage.

The temperature dependent structural evolutions of RbxC60 (x = 3, 5, 6) and K4C60 were studied using both in-house andsynchrotron x-ray powder diffraction and thermal analysis techniques over a temperature range of 10K - 673K. The superconducting face centered-cubic (fcc) Rb3C60 and the body centered-tetragonal (bct) M4C60(M = K, Rb) phases are found to be line compounds in this temperature range, while the body centered-cubic (bcc) phase forms a solid solution in which the solubility of vacant M sites increases with temperature. The orientation of the C60 molecules in the K4C60 phase was analyzed. A crystalline fcc Rb1C60 phase is stable only above room temperature.

A force constant model for the vibrational modes in C60, based on bond-stretching and anglebending interactions, is presented. The results of this model are compared with the experimental data available from Raman, infrared, and high resolution electron energy loss spectroscopies, as well as neutron inelastic scattering measurements. Excellent agreement is obtained between the calculated and experimental mode frequencies. The pressure dependence of the Ramanand infrared-active mode frequencies is calculated within a simple model and is compared to available experimental data.

The nucleation and cluster growth of C60 and C70 crystallites on various substrates at ambient temperature have been investigated using electron microscopy. It was found that the initial nucleation is closely associated with surface defects, and the fullerenes are much more strongly bonded to each other than to the substrate. Sublimed C60 or C70 crystallites nucleate at the step edge in the liquid state and are aligned with the step walls and terraces through the process of coalescence. Reflection Electron Microscopy (REM) studies have shown an abnormal profile of C60 grown crystals as a result of the interaction of C60 molecules with the surface strain field during crystal growth. Transmission electron diffraction patterns reveal a twin structure with (110) habit plane for the low temperature ordered phase.

We present first-principles local density functional calculations of the electronic structure and energetics of neutral and negatively charged fullerene molecules. We find thatthe negatively charged -1 state is stable relative to the neutral molecule and that the -2 state is stable relative to the neutral molecule but not to the -1 state of the molecule. We have also performed calculations of the electronic polarizabilities for different charged states and developed a simple model to estimate the dielectric constant of fullerene based crystals.

Purely carbonaceous aggregates C20 have been studied by the AM1 quantumchemical method. In addition to one dodecahedron-shaped structure possessing C1 symmetry another three-dimensional species is revealed, viz. a bowl-shaped structureof C5v symmetry (and also one two-dimensional and two one-dimensional species). Temperature dependence of the relative stabilities of both three-dimensional structures is evaluated, showing that in the relevant temperature region the fullerenic species is prevailing. However, in a very high temperature region a relative-stability interchange has been predicted.

The low energy part of the linear optical response spectrum and lowest order hyperpolarizability γ(3) of C60 are calculated by a sum over state approach using single particle wavefunctions and. energy levels determined from local density calculations. Lorentz local field factors, as well as a RPA correction are introducedto facilitate comparison with the dielectric function ε(ω) determined fromfilms of C60. γ( 2 ) for a centrosymmetric molecule such asC60 is zero and the lowest non-zero contribution to the polarizability is γ( 3 ). Reasonable agreement is found with linear optical response experiments if a RPA screening is used. However, SHG and THG experiments on C60 in solid or solution form, yields values closer to the unscreened results.

We have developed an automatic computational method for generating graphitic carbon structures. We propose models for crystalline and amorphous forms of carbon consisting of a single negatively curved graphitic sheet forming an extended structure. Stability and elastic properties are computed using an energy estimate fit to local density approximation(LDA) calculations. These forms of carbon are found to be more stable than C60. The radial distribution function for the random structures closely matches that of films of amorphous carbon grown on NaCI substrates from sublimated graphite.

We report angle-resolved photoemission data from single crystals of C60 cleaved in UHV. Unlike the other forms of pure carbon, the valence band spectrum of C60 consists of many sharp features that can be essentially accounted for by the quantum chemical calculations describing individual molecules. This suggests that the electronic structure of solid C60 is mainly determined by the bonding interactions within the individual molecules. We also observe remarkable intensity modulations of the photoemission features as a function of photon energy, suggesting strong final state effects. Finally, we address the issue of the band width of the HOMO state of C60. We assert that the width of the photoemission peak of C60 does not reflectthe intrinsic band width.

An efficient aqueous acid chemistry for the preparation of fullerols, consisting of 14-15 hydroxyl moieties in an average structure, from C60 molecules is described.

Endohedral fullerenes were first observed in molecular beams produced in laser vaporizations sources.[1] Since the discovery of the arc method [2] of producing large quantities of fullerenes several laboratories have been searching for methods to produce and isolate sufficient quantities of endohedral fullerenes to permit the study of their unique material properties.

The 13C NMR of FCC C60 under magic angle spinning (MAS) conditionsyields linewidths on the order of 1 Hz at fields of 4.7 T. The spectrum consists of a primary resonance at 143.7 ppm and a minor peak shifted 0.7 ppm downfield. The intensity of the minor resonance relative to the primary resonance was found to vary from 0.6 to 5.5 % depending on the sample history. The downfield shift obeys Curie's law and isattributed to the Fermi contact coupling interaction between paramagnetic oxygen molecules and all 60 carbon atoms of rapidly rotating adjacent C60 molecules. Exposure of the sample to 1 kbar oxygen for 1 3/4 hours resulted in a spectrum of 7 evenly spaced resonances corresponding to 0 to 6 of the adjacent octahedral interstitial sites being filled with oxygen molecules. At ambient pressure, the oxygen diffused out of the lattice on time scales ranging from hours to days.

We report here the arc-production and spectroscopic characterization of fullerene-encapsulated metal atoms and metal-atom clusters. In particular, both solution and solid-stateelectron paramagnetic resonance (EPR) spectra of LaC82', YC82', SCC82' and Sc3 C82 have been obtained. Additional species containing rareearth atoms and clusters have been produced. The results suggest, for example, that the three scandium atoms in Sc3C82 form a molecule In the shape of an equilateral triangle — as was previously suggested for Sc3 molecules Isolated In a cryogenic rare-gas matrix. The spectraof the MC82 species (M =La, Y, Sc) exhibit small hyperfine couplings and g-values close to 2, suggesting that they can be described as a +3 metal cations within – 3 fullerene radical anion cages. Sc2C2n species — the most abundant metailofuilerenes In the scandlum-fullerene mass spectrum — are EPR-silent, even though Sc2 is EPR-actlve In a rare-gas matrix at 4.2K. A broader Implication of this work Is that production of macroscopic quantities of metal-containing fullerenes may make possible the fabrication of exotic new structures with regular arrays of metal atoms or clusters Isolated in fullerene molecules, resulting in new typesof host/guest nanostructured materials.

Fullerenes with a metal atom inside of the cage, metallofulierenes, were produced by either laser vaporization or a graphite arc and characterized using a variety of mass spectrometric methods. First, yttrium-fullerene adducts were formed by direct laser vaporization of samples consisting of graphite, yttrium oxide and fullerenes. Fragmentation and oxidation ion/molecule reactions showed that the laser-generated adducts are endohedral complexes (Yx@Cn), in contrast to externally-bound Y(Cn)+ species formed by gas-phase reactions. In addition, evidence was obtained for laserinduced bulk coalescence reactions yielding the metallofullerenes. Second, negative ion/desorption chemical ionization mass spectrometry was used to characterize metallofullerenes in arc-generated soot, pyridine extracts and the extract residue. The pyridine extracts of La2O3/graphite soot contain mostlyLa@C82 and La2@C80', in addition to (empty) fullerenes. However, the raw soot and the extract residue contain a broader range of metallofullerenes with relative abundances different than those observed from the extract (e.g. abundant La@C60', Lax@Cn') and La@C74). The thermal desorption behavior of the doped and undoped fullerenes indicate an interaction between the Cn and Lax@Cn species. Analysis of aqueous solutions of dried pyridine extracts of La2O3/graphite soot show Cn and Lax;@Cn' which is consistent with the possible presence ofmetallofullerene/ fullerene ionic complexes, (Lax@Cn)+C-n.

We review results of our local-density-functional-based cluster calculations and molecular dynamics simulations of fullerenes and related structures. These include predictions of cohesive energies, electronic structures, and photoelectron spectra for a number of pure and chemically substituted fullerenes, studies of the resilience of C60 under severe compression and during surface collisions, simulations of the trapping of Hein the interior of C60, predictions of the strain energy, electronic and elastic properties of graphitic tubules, and simulations of the folding and curling of graphitic ribbons.