Disentangling the multiorbital contributions of excitons by photoemission exciton tomography.

Excitons are realizations of a correlated many-particle wave function, specifically consisting of electrons and holes in an entangled state. Excitons occur widely in semiconductors and are dominant excitations in semiconducting organic and low-dimensional quantum materials. To efficiently harness the strong optical response and high tuneability of excitons in optoelectronics and in energy-transformation processes, access to the full wavefunction of the entangled state is critical, but has so far not been feasible. Here, we show how time-resolved photoemission momentum microscopy can be used to gain access to the entangled wavefunction and to unravel the exciton's multiorbital electron and hole contributions. For the prototypical organic semiconductor buckminsterfullerene (C60), we exemplify the capabilities of exciton tomography and achieve unprecedented access to key properties of the entangled exciton state including localization, charge-transfer character, and ultrafast exciton formation and relaxation dynamics.

Charge and adsorption height dependence of the self-metalation of porphyrins on ultrathin MgO(001) films.

We have experimentally determined the adsorption structure, charge state, and metalation state of porphin, the fundamental building block of porphyrins, on ultrathin Ag(001)-supported MgO(001) films by scanning tunneling microscopy and photoemission spectroscopy, supported by calculations based on density functional theory. By tuning the substrate work function to values below and above the critical work function for charging, we succeeded in the preparation of 2H-P monolayers which contain negatively charged and uncharged molecules. It is shown that the porphin molecules self-metalate at room temperature, forming the corresponding Mg-porphin, irrespective of their charge state. This is in contrast to self-metalation of tetraphenyl porphyrin (TPP), which occurs on planar MgO(001) only if the molecules are negatively charged. The different reactivity is explained by the reduced molecule-substrate distance of the planar porphin molecule compared to the bulkier TPP. The results of this study shed light on the mechanism of porphyrin self-metalation on oxides and highlight the role of the adsorption geometry on the chemical reactivity.

Large Distortion of Fused Aromatics on Dielectric Interlayers Quantified by Photoemission Orbital Tomography.

Polycyclic aromatic compounds with fused benzene rings offer an extraordinary versatility as next-generation organic semiconducting materials for nanoelectronics and optoelectronics due to their tunable characteristics, including charge-carrier mobility and optical absorption. Nonplanarity can be an additional parameter to customize their electronic and optical properties without changing the aromatic core. In this work, we report a combined experimental and theoretical study in which we directly observe large, geometry-induced modifications in the frontier orbitals of a prototypical dye molecule when adsorbed on an atomically thin dielectric interlayer on a metallic substrate. Experimentally, we employ angle-resolved photoemission experiments, interpreted in the framework of the photoemission orbital tomography technique. We demonstrate its sensitivity to detect geometrical bends in adsorbed molecules and highlight the role of the photon energy used in experiment for detecting such geometrical distortions. Theoretically, we conduct density functional calculations to determine the geometric and electronic structure of the adsorbed molecule and simulate the photoemission angular distribution patterns. While we found an overall good agreement between experimental and theoretical data, our results also unveil limitations in current van der Waals corrected density functional approaches for such organic/dielectric interfaces. Hence, photoemission orbital tomography provides a vital experimental benchmark for such systems. By comparison with the state of the same molecule on a metallic substrate, we also offer an explanation why the adsorption on the dielectric induces such large bends in the molecule.

Charge-Promoted Self-Metalation of Porphyrins on an Oxide Surface.

Metalation and self-metalation reactions of porphyrins on oxide surfaces have recently gained interest. The mechanism of porphyrin self-metalation on oxides is, however, far from being understood. Herein, we show by a combination of results obtained with scanning tunneling microscopy, photoemission spectroscopy, and DFT computations, that the self-metalation of 2H-tetraphenylporphyrin on the surface of ultrathin MgO(001) films is promoted by charge transfer. By tuning the work function of the MgO(001)/Ag(001) substrate, we are able to control the charge and the metalation state of the porphyrin molecules on the surface.