Daniel Lüftner

Unexpected interplay of bonding height and energy level alignment at heteromolecular hybrid interfaces

Although geometric and electronic properties of any physical or chemical system are always mutually coupled by the rules of quantum mechanics, counterintuitive coincidences between the two are sometimes observed. The coadsorption of the organic molecules 3,4,9,10-perylene tetracarboxylic dianhydride and copper-II-phthalocyanine on Ag(111) represents such a case, since geometric and electronic structures appear to be decoupled: one molecule moves away from the substrate while its electronic structure indicates a stronger chemical interaction, and vice versa for the other. Our comprehensive experimental and ab-initio theoretical study reveals that, mediated by the metal surface, both species mutually amplify their charge-donating and -accepting characters, respectively. This resolves the apparent paradox, and demonstrates with exceptional clarity how geometric and electronic bonding parameters are intertwined at metal-organic interfaces.

Imaging the wave functions of adsorbed molecules

Significance In quantum mechanics, the electrons in a molecule are described by a mathematical object termed the wave function or molecular orbital. This function determines the chemical and physical properties of matter and consequently there has been much interest in measuring orbitals, despite the fact that strictly speaking they are not quantum-mechanical observables. We show how the amplitude and phase of orbitals can be measured in good agreement with wave functions from ab initio calculations. Not only do such measurements allow wave functions of complex molecules and nanostructures to be determined, they also open up a window into critical discussions of theoretical orbital concepts. The basis for a quantum-mechanical description of matter is electron wave functions. For atoms and molecules, their spatial distributions and phases are known as orbitals. Although orbitals are very powerful concepts, experimentally only the electron densities and -energy levels are directly observable. Regardless whether orbitals are observed in real space with scanning probe experiments, or in reciprocal space by photoemission, the phase information of the orbital is lost. Here, we show that the experimental momentum maps of angle-resolved photoemission from molecular orbitals can be transformed to real-space orbitals via an iterative procedure which also retrieves the lost phase information. This is demonstrated with images obtained of a number of orbitals of the molecules pentacene (C22H14) and perylene-3,4,9,10-tetracarboxylic dianhydride (C24H8O6), adsorbed on silver, which are in excellent agreement with ab initio calculations. The procedure requires no a priori knowledge of the orbitals and is shown to be simple and robust.

Energy offsets within a molecular monolayer: the influence of the molecular environment

The compressed 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) herringbone monolayer structure on Ag(110) is used as a model system to investigate the role of molecule–molecule interactions at metal–organic interfaces. By means of the orbital tomography technique, we can not only distinguish the two inequivalent molecules in the unit cell but also resolve their different energy positions for the highest occupied and the lowest unoccupied molecular orbitals. Density functional theory calculations of a freestanding PTCDA layer identify the electrostatic interaction between neighboring molecules, rather than the adsorption site, as the main reason for the molecular level splitting observed experimentally.

Orbital tomography of hybridized and dispersing molecular overlayers

With angle resolved photoemission experiments and \emph{ab-initio} electronic structure calculations, the pentacene monolayers on Ag(110) and Cu(110) are compared and contrasted allowing the molecular orientation and an unambiguous assignment of emissions to specific orbitals to be made. On Ag(110), the orbitals remain essentially isolated-molecule like, while strong substrate-enhanced dispersion and orbital modification are observed upon adsorption on Cu(110). We show how the photoemission intensity of extended systems can be simulated and that it behaves essentially like that of the isolated molecule modulated by the band dispersion due to intermolecular interactions.

Experimental and theoretical electronic structure of quinacridone

The energy positions of frontier orbitals in organic electronic materials are often studied experimentally by (inverse) photoemission spectroscopy and theoretically within density functional theory. However, standard exchange-correlation functionals often result in too small fundamental gaps, may lead to wrong orbital energy ordering, and do not capture polarization-induced gap renormalization. Here we examine these issues and a strategy for overcoming them by studying the gas phase and bulk electronic structure of the organic molecule quinacridone (5Q), a promising material with many interesting properties for organic devices. Experimentally we perform angle-resolved photoemission spectroscopy (ARUPS) on thin films of the crystalline

Exploring three-dimensional orbital imaging with energy-dependent photoemission tomography

\ensuremath{\beta}

Epitaxy of highly ordered organic semiconductor crystallite networks supported by hexagonal boron nitride

phase of 5Q. Theoretically we employ an optimally tuned range-separated hybrid functional (OT-RSH) within density functional theory. For the gas phase molecule, our OT-RSH result for the ionization potential (IP) represents a substantial improvement over the semilocal PBE and the PBE0 hybrid functional results, producing an IP in quantitative agreement with experiment. For the bulk crystal we take into account the correct screening in the bulk, using the recently developed optimally tuned screened range-separated hybrid (OT-SRSH) approach, while retaining the optimally tuned parameters for the range separation and the short-range Fock exchange. This leads to a band gap narrowing due to polarization effects and results in a valence band spectrum in excellent agreement with experimental ARUPS data, with respect to both peak positions and heights. Finally, full-frequency

Energy Ordering of Molecular Orbitals

{G}_{0}{W}_{0}

Charge Transfer and Orbital Level Alignment at Inorganic/Organic Interfaces: The Role of Dielectric Interlayers

results based on a hybrid functional starting point are shown to agree with the OT-SRSH approach, improving substantially on the PBE-starting point.

Multi-orbital charge transfer at highly oriented organic/metal interfaces

Recently, it has been shown that experimental data from angle-resolved photoemission spectroscopy on oriented molecular films can be utilized to retrieve real-space images of molecular orbitals in two dimensions. Here, we extend this orbital tomography technique by performing photoemission initial state scans as a function of photon energy on the example of the brickwall monolayer of 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) on Ag(110). The overall dependence of the photocurrent on the photon energy can be well accounted for by assuming a plane wave for the final state. However, the experimental data, both for the highest occupied and the lowest unoccupied molecular orbital of PTCDA, exhibits an additional modulation attributed to final state scattering effects. Nevertheless, as these effects beyond a plane wave final state are comparably small, we are able, with extrapolations beyond the attainable photon energy range, to reconstruct three-dimensional images for both orbitals in agreement with calculations for the adsorbed molecule.