Lisbeth Kjeldgaard

The electronic structure of iron phthalocyanine probed by photoelectron and x-ray absorption spectroscopies and density functional theory calculations

A joint experimental and theoretical work to explain the electronic and geometrical structure of an in situ prepared film of iron phthalocyanine (FePc) on silicon (100) is presented. FePc molecular films have been characterized by core and valence photoemission spectroscopy (PES) and x-ray absorption spectroscopy (XAS), and the results have been interpreted and simulated by density functional theory (DFT) calculations. C1s and N1s PE spectra have been analyzed by taking into account all chemically nonequivalent C and N atoms in the molecule. In the Fe2p(32) spectra it has been possible to resolve two components that can be related to the open shell structure of the molecule. By valence PES and N1s XAS data, the geometrical orientation of the FePc molecules in the film could be determined. Our results indicate that for the FePc on Si(100), the molecules within the film are mainly standing on the surface. The experimental N1s XAS spectra are very well reproduced by the theoretical calculations, which are both angle and atomic resolved, giving a detailed description of the electronic and geometric structure of the FePc film. Furthermore, the asymmetry and the intensity angle variation of the first N1s XAS threshold feature could be explained by the presented DFT calculations as due to the chemical nonequivalence of the N atoms and the symmetry character of the lowest unoccupied molecular orbital.

Electronic structure of a vapor-deposited metal-free phthalocyanine thin film

The electronic structure of a vapor-sublimated thin film of metal-free phthalocyanine (H2Pc) is studied experimentally and theoretically. An atom-specific picture of the occupied and unoccupied electronic states is obtained using x-ray-absorption spectroscopy (XAS), core- and valence-level x-ray photoelectron spectroscopy (XPS), and density-functional theory (DFT) calculations. The DFT calculations allow for an identification of the contributions from individual nitrogen atoms to the experimental N1s XAS and valence XPS spectra. This comprehensive study of metal-free phthalocyanine is relevant for the application of such molecules in molecular electronics and provides a solid foundation for identifying modifications in the electronic structure induced by various substituent groups.

Excited-state charge transfer dynamics in systems of aromatic adsorbates on TiO2 studied with resonant core techniques

Resonant core spectroscopies are applied to a study of the excited electron transfer dynamics on a low-femtosecond time scale in systems of aromatic molecules (isonicotinic acid and bi-isonicotinic acid) adsorbed on a rutile TiO 2 (110) semiconductor surface. Depending on which adsorbate state is excited, the electron is either localized on the adsorbate in an excitonic effect, or delocalizes rapidly into the substrate in less than 5 fs (3 fs) for isonicotinic acid (bi-isonicotinic acid). The results are obtained by the application of a variant of resonant photoemission spectroscopy.

Synchrotron radiation study of the electronic structure of multiwalled carbon nanotubes

We present photoelectron (PE) and x-ray absorption spectra (XAS) of macroscopically aligned multiwalled carbon nanotubes. We identify the peaks in the valence PE spectra with regions of high density of states through comparison to calculations for graphite. Finally, we outline and illustrate a simple method for using XAS to determine the average alignment of a nanotube sample.

Origin of molecular orbital splitting of C-60 on Al(110)

We have investigated the C-60 monolayer on Al(l 10) with angle-dependent photoelectron spectroscopy. We find that orbital components have different angular distributions. Calculations of cross sections of the highest occupied molecular orbital components for free, oriented C-60 are found to describe the experimental data quite well. The observed band splitting is attributed to intramolecular electronic correlations, due to the different coupling of the orbital components to the substrate conduction band.

Insulating surface layer on single crystal K3C60

Abstract.Using angle-dependent photoemission spectra of core and valence levels we show that metallic, single crystal K3C60 is terminated by an insulating or weakly-conducting surface layer. We attribute this to the effects of strong intermolecular correlations combined with the average surface charge state. Several controversies on the electronic structure are thereby resolved.

Angle-dependent valence photoemission study of pure phase K3C60

We have carried out angle-dependent PES measurements of pure phase K3C60 films prepared in UHV. The shape of the valence spectrum shows a quite strong angle-dependence which was unobserved in previous studies. We attribute this to the important role of the light polarization. We show that there is a strong bulk contribution at the Fermi level.