This work concerns the interaction of intense, ultrashort laser pulses with fullerenes and carbon nanotubes. This includes the excitation and ionisation dynamics of gas phase fullerenes and the response of carbon nanotubes to intense ultrashort laser pulses. When ionising C60 with laser pulses of duration between 50 fs up to a few hundred fs, the ionisation mechanism has been proposed to be thermal in nature, with the electronic subsystem ‘hot’ and the vibrational system ‘cold’ at the time of ionisation. Recent results show an anisotropy in the photoelectron angular distribution which may suggest more direct mechanisms at work. Velocity-Map Imaging photoelectron spectroscopy results are presented for the ionisation of C60 and C70 at various wavelengths, pulse durations and intensities and the results are compared to theoretical models. The results are described well by a thermal ionisation mechanism in which a significant number of electrons are emitted during the laser pulse. Electrons may gain a momentum ‘kick’ from the electric field of the laser which results in an anisotropy in the photoelectron angular distributions. Peaks are observed, superimposed on the thermal background, in the photoelectron kinetic energy spectra of fullerenes ionised by ultrashort laser pulses which were previously assigned as Rydberg peaks. Photoelectron angular distributions of these peaks are presented for C60 and C70 ionised with laser pulses of various wavelengths. The binding energies and anisotropy parameters fitted to the peaks suggest that they are due to the population and one-photon ionisation of superatom molecular orbitals (SAMOs). The results rule out a direct multiphoton population mechanism for these states and show many similarities with Rydberg fingerprint spectroscopy. The fusion of carbon nanotubes has been observed under high energy electron beams and fullerene molecules have been shown to fuse together after irradiation with ultrashort laser pulses. Results are presented for experiments where fusion of carbon nanotubes with ultrashort laser pulses was attempted. Thin carbon nanotube films are analysed via Raman spectroscopy after irradiation by single laser pulses. A number of low frequency radial breathing mode peaks were observed which suggest that fusion may have taken place at certain areas of the sample.

This thesis is based on two main parts. The first part concerns purification and functionalization of carbon nanotubes (papers I-III), and the second part is related to the synthesis of organometallic fullerene derivatives (papers IV-VII): Two oxidative methods involving aqueous nitric acid were compared with respect to their capability to introduce carboxylic groups into single walled carbon nanotubes, and several literature methods for esterification and amidation of these groups have been evaluated with focus on efficiency and reproducibility in forming covalently functionalized products soluble in organic media. Amidation proceeding via a SWNT-(COCl)n intermediate yielded the expected covalent product, whereas carboxylate salt formation dominated with other attempted methods. Esterification was achieved via the acyl chloride method and via alkylation of SWNT-(COO–)n, the latter being the more efficient method. A new, reagent-free method for purification of single- and multi walled carbon nanotubes has been developed. Microwave treatment dissociates non-nanotube carbon and disperses it into an organic solvent, resulting in very pure carbon nanotubes within a few minutes of heating, without the involvement of acidic/oxidative reagents. According to thermogravimetric analysis, Raman and IR spectroscopy, as well as SEM, the process yields nanotubes with a low degree of defects. A non-covalent approach has been employed to prepare nanotubes functionalized with glycosides. Derivatives of galactose and lactose were covalently linked to a pyrene moiety and the thus formed pyrene-glycosides were non-covalently attached to single- and multi walled carbon nanotubes by π-π interactions. Fluorescence titrations have been used to quantify the formed supramolecular assemblies, which for SWNTs exhibits increased water solubility. A fulleropyrrolidine-(tricarbonyl)chromium complex was synthesized and fully characterized. IR spectroelectrochemistry was used to probe the redox state of the fullerene and provided evidence for electronic communication between the two electroacive moieties. A C60-ferrocene-C60 triad system was synthesized and characterized. Cyclic voltammetry and fluorescence studies suggested electronic communication between ferrocene and the two fullerenes. Finally, the synthesis and initial characterization of short fullerene-ferrocene oligomers are presented.

Thesis (Ph. D.)--Oregon State University, 2008. / Printout. Includes bibliographical references (leaves 122-129). Also available on the World Wide Web.

Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2008. / "[pi]" appears in the title as a symbol. Includes bibliographical references. Also available in electronic version.

Diss. (sammanfattning) Göteborg : Univ. , 2010. / Härtill 5 uppsatser.

Thesis (Ph.D.)--Civil and Environmental Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Jae-Hong Kim; Committee Member: Joseph hughes; Committee Member: Michael Bergin; Committee Member: Seung Soon Jang; Committee Member: Vernon Snoeyink.

Includes bibliographical references.

The chemistry of fullerenes, which are a class of carbon allotropes that can be prepared by vaporization of graphite in an electric arc in a low pressure atmosphere,1 has become a topic of much experimental and theoretical study over the past 25 years.  Herein we present a series of theoretical studies related to recently discovered or studied endohedral metallofullerenes (EMF) and a theory as to the selective stability of certain isomers of EMFs. Computational treatments of the anions of C80 and C94 are presented and compared in an effort to gain an understanding and predictive model for which isomers of each cage size EMF will be most stable.  A model is proposed in which the pentagons of fullerene anions are seen as charge localization centers that repel one another, making the pyracyclene bonding motif much more unstable for fullerene anions than for fullerene neutral cages. Computational treatments are also presented for two newly discovered EMFs, Y2C2@C92 and Gd2@C79N.  Y2C2@C92 is reported to exhibit a previously undiscovered mode of internal cluster rotation, while Gd2@C79N is shown to have unusual stability for an azofullerene with a large spin quantum number (15/2). Finally, computational techniques are employed to predict the thermodynamic feasibility of a chemical reaction replacing one metal atom in a trimetallic-nitride template (TNT) endohedral metallofullerene with different metal atom.  At least two of these are predicted to be thermodynamically practical. / Ph. D.

No description available.

Acquiring in depth knowledge of the ozone oxidation of surface-bound fullerenes advances the understanding of fullerene fate in the environment, as well as the reactivity of ozone with carbonaceous nanomaterials. Recent ultrahigh vacuum studies of the reaction of gasphase ozone with surface-bound fullerenes have made it possible to observe the formation and subsequent thermal decomposition of the primary ozonide (PO). As the use of nanomaterials, such as C₆₀, continues to increase, the exposure of these molecules to humans and the environment is of growing concern, especially if they can be chemically altered by common pollutants. These experiments are made possible by combining ultrahigh vacuum surface analysis techniques with precision dosing using a pure O₃ gas source. The experimental setup also provides the capability of monitoring surface-bound reactants and products in situ with reflection-absorption IR spectroscopy, while gas-phase products are detected with a mass spectrometer. Our results indicate that ozone adds across a 6/6 bond on the C₆₀ cage, forming an unstable intermediate, the primary ozonide. The observed initial reaction probability for the PO is γ = 4.1 x 10⁻³. Energies of activation for the formation and decomposition of the PO were obtained via temperature-dependent studies. After formation, the primary ozonide thermally decomposes into the Criegee Intermediate which can rearrange or, upon further exposure to ozone, react with another ozone molecule to form a variety of products such as carbonyls, anhydrides, esters, ethers, and ketenes. Larger fullerenes (C₇₀, C₇₆, C₇₈, and C₈₄) were also exposed to gas-phase ozone, in order to observe the reaction rate for ozonolysis and to propose an initial mechanism for ozone exposure. The results indicate that the structure of the fullerenes has little to no impact on the rate of oxidation via ozone. Lastly, Terbium endohedral were exposed to ozone, in an effort to determine whether ozone was capable of oxidizing both the outer fullerene cage, as well as the Tb atom sequestered inside. The preliminary XPS data suggests ozone oxidizes both within an hour of continuous exposure. Understanding this atmospherically-relevant reaction from both a mechanistic and kinetic standpoint will help predict the environmental fate of fullerenes and their oxides. / Ph. D.