RESUMEN
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.
RESUMEN
Angular-resolved photoelectron spectroscopy using wavelength-tuneable femtosecond laser pulses is presented for a series of fullerenes, namely, C70, C82, and Sc3N@C80. The photoelectron kinetic energy distributions for the three molecules show typical thermal electron spectra with a superimposed peak structure that is the result of one-photon ionization of diffuse low-angular momenta states with electron density close to the carbon cage and that are related to so-called super atom molecular orbitals. Photoelectron angular distributions confirm this assignment. The observed structure is less prominent compared to the thermal electron background than what was observed in C60. It can be concluded that hot electron emission is the main ionization channel for the larger and more complex molecules for these excitation conditions.
RESUMEN
Super-atom molecular orbitals are orbitals that form diffuse hydrogenic excited electronic states of fullerenes with their electron density centred at the centre of the hollow carbon cage and a significant electron density inside the cage. This is a consequence of the high symmetry and hollow structure of the molecules and distinguishes them from typical low-lying molecular Rydberg states. This review summarizes the current experimental and theoretical studies related to these exotic excited electronic states with emphasis on femtosecond photoelectron spectroscopy experiments on gas-phase fullerenes.This article is part of the themed issue 'Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene'.