TD-DFT calculations of low-lying, Rydberg states of a series of polycyclic hydrocarbons and cyclic alkanes are presented. Systematic variations in binding energies and photoelectron angular distributions for the first members of the s, p and d Rydberg series are predicted for increasing molecular complexity. Calculated binding energies are found to be in very good agreement with literature values where they exist for comparison. Experimental angle-resolved photoelectron spectroscopy results are presented for coronene, again showing very good agreement with theoretical predictions of binding energies and also for photoelectron angular distributions. The Dyson orbitals for the small “hollow” carbon structures, cubane, adamantane and dodecahedrane, are shown to have close similarities to atomic s, p and d orbitals, similar to the superatom molecular orbitals (SAMOs) reported for fullerenes, indicating that these low-lying, diffuse states are not restricted to π-conjugated molecules.

The electronic structure and photoinduced dynamics of fullerenes, especially C60, is of great interest because these molecules are model systems for more complex molecules and nanomaterials. In this work we have used Rydberg Fingerprint Spectroscopy to determine the relative ionization intensities from excited SAMO (Rydberg-like) states in C60 as a function of laser wavelength. The relative ionization intensities are then compared to the ratio of the photoionization widths of the Rydberg-like states, computed in time-dependent density functional theory (TD-DFT). The agreement is remarkably good when the same photon order is required to energetically access the excited states. This illustrates the predictive potential of quantum chemistry for studying photoionization of large, complex molecules as well as confirming the assumption that is often made concerning the multiphoton excitation and rapid energy redistribution in the fullerenes.

Gas-phase fullerenes emit thermal electrons after femtosecond laser excitation in the wavelength range 400–800 nm. We have used angular-resolved photoelectron spectroscopy (PES) to study the influence of the laser’s electric field on the dynamics of the thermally emitted electrons. The laser field introduces an asymmetry in the thermal electron distributions with respect to the laser polarization direction, which was confirmed by carrying out experiments at different wavelengths. A simple model could reproduce the trends in measured apparent temperatures in the PES. The asymmetry effect was exploited in a pump–probe experiment to estimate the time scale for thermal electron emission. It was found that, when 400 nm, 120 fs laser pulses of 2 TW cm–2 intensity are used, thermal electrons are emitted up to ca. 300 fs after the peak of the laser pulse. The pump–probe scheme should be applicable to a wider range of complex molecules and clusters showing thermal electron emission on a femtosecond time scale.

Fullerenes are interesting model systems for probing the complex, fundamental electron dynamics and ionisation mechanisms of large molecules and nanoparticles. In this Tutorial Review we explain how recent experimental and theoretical advances are providing insight into the interesting phenomenon of thermal electron emission from molecular systems and the properties of hydrogenic, diffuse, excited electronic states, known as superatom molecular orbitals, which are responsible for relatively simple, well-resolved structure in fs laser photoelectron spectra of fullerenes. We focus on the application of velocity map imaging combined with fs laser photoionisation to study angular-resolved photoelectron emission.

We demonstrate an electrically tunable 2D photonic crystal array constructed from vertically aligned carbon nanofibers. The nanofibers are actuated by applying a voltage between adjacent carbon nanofiber pairs grown directly on metal electrodes, thus dynamically changing the form factor of the photonic crystal lattice. The change in optical properties is characterized using optical diffraction and ellipsometry. The experimental results are shown to be in agreement with theoretical predictions and provide a proof-of-principle for rapidly switchable photonic crystals operating in the visible that can be fabricated using standard nanolithography techniques combined with plasma CVD growth of the nanofibers.

Classical continuum mechanics is used extensively to predict the properties of nanoscale materials such as graphene. The bending rigidity, κ, is an important parameter that is used, for example, to predict the performance of graphene nanoelectromechanical devices and also ripple formation. Despite its importance, there is a large spread in the theoretical predictions of κ for few-layer graphene. We have used the snap-through behavior of convex buckled graphene membranes under the application of electrostatic pressure to determine experimentally values of κ for double-layer graphene membranes. We demonstrate how to prepare convex-buckled suspended graphene ribbons and fully clamped suspended membranes and show how the determination of the curvature of the membranes and the critical snap-through voltage, using AFM, allows us to extract κ. The bending rigidity of bilayer graphene membranes under ambient conditions was determined to be 35.5–15.0+20.0 eV. Monolayers are shown to have significantly lower κ than bilayers.

Novel field effect transistors with suspended graphene gates are demonstrated. By incorporating mechanical motion of the gate electrode, it is possible to improve the switching characteristics compared to a static gate, as shown by a combination of experimental measurements and numerical simulations. The mechanical motion of the graphene gate is confirmed by using atomic force microscopy to directly measure the electrostatic deflection. The device geometry investigated here can also provide a sensitive measurement technique for detecting high-frequency motion of suspended membranes as required, e.g., for mass sensing.

We report the effect of catalyst pattern geometry on the growth behaviour of carbon nanotube (CNT) vertical arrays. Larger patterns are seen to produce longer CNT arrays. We show that this is predominantly related to the pattern size dependence of the number of walls and relate this to the local availability of carbon feedstock species. In addition, the vertical alignment of CNT pillar arrays is seen to depend on the pattern design, in particular the relationship between the pillar dimension and the inter-pillar spacing.

A direct on-chip transmission measurement of the resonance frequency of an individual singly clamped carbon nanofiber relay is reported. The experimental results are in good agreement with a small signal model and show the expected tuning of the resonance frequency with changing bias voltage.

Fullerenes are interesting model systems for probing the complex, fundamental electron dynamics and ionisation mechanisms of large molecules and nanoparticles. In this Tutorial Review we explain how recent experimental and theoretical advances are providing insight into the interesting phenomenon of thermal electron emission from molecular systems and the properties of hydrogenic, diffuse, excited electronic states, known as superatom molecular orbitals, which are responsible for relatively simple, well-resolved structure in fs laser photoelectron spectra of fullerenes. We focus on the application of velocity map imaging combined with fs laser photoionisation to study angular-resolved photoelectron emission.