Simulation of angle-resolved photoemission spectra by approximating the final state by a plane wave: From graphene to polycyclic aromatic hydrocarbon molecules

AbstractWe present a computational study on the angular-resolved photoemission spectra (ARPES) from a number of polycyclic aromatic hydrocarbons and graphene. Our theoretical approach is based on ab-initio density functional theory and the one-step model where we greatly simplify the evaluation of the matrix element by assuming a plane wave for the final state. Before comparing our ARPES simulations with available experimental data, we discuss how typical approximations for the exchange-correlation energy affect orbital energies. In particular, we show that by employing a hybrid functional, considerable improvement can be obtained over semi-local functionals in terms of band widths and relative energies of π and σ states. Our ARPES simulations for graphene show that the plane wave final state approximation provides indeed an excellent description when compared to experimental band maps and constant binding energy maps. Furthermore, our ARPES simulations for a number of polycyclic aromatic molecules from the oligo-acene, oligo-phenylene, phen-anthrene families as well as for disc-shaped molecules nicely illustrate the evolution of the electronic structure from molecules with increasing size towards graphene

Photoemission Orbital Tomography for Excitons in Organic Molecules

Driven by recent developments in time-resolved photoemission spectroscopy, we extend the successful method of photoemission orbital tomography (POT) to excited states. Our theory retains the intuitive orbital picture of POT, while respecting both the entangled character of the exciton wave function and the energy conservation in the process. Analyzing results from three organic molecules, we classify generic exciton structures and give a simple interpretation in terms of natural transition orbitals. We validate our findings by directly simulating pump-probe experiments with time-dependent density functional theory.Comment: 28 pages, 8 figure

Band renormalization of a polymer physisorbed on graphene investigated by many-body perturbation theory

Many-body perturbation theory at the $G_0W_0$ level is employed to study the electronic properties of poly(\emph{para}-phenylene) (PPP) on graphene. Analysis of the charge density and the electrostatic potential shows that the polymer-surface interaction gives rise to the formation of only weak surface dipoles with no charge transfer between the polymer and the surface. In the local-density approximation (LDA) of density-functional theory, the band structure of the combined system appears as a superposition of the eigenstates of its constituents. Consequently, the LDA band gap of PPP remains unchanged upon adsorption onto graphene. $G_0W_0$ calculations, however, renormalize the electronic levels of the weakly physisorbed polymer. Thereby, its band gap is considerably reduced compared to that of the isolated PPP chain. This effect can be understood in terms of image charges induced in the graphene layer, which allows us to explain the quasi-particle gap of PPP versus polymer-graphene distance by applying a classical image-potential model. For distances below 4.5 {\AA}, however, deviations from this simple classical model arise which we qualitatively explain by taking into account the polarizablity of the adsorbate. For a quantitative description with predictive power, however, we emphasize the need for an accurate ab-initio description of the electronic structure for weakly coupled systems at equilibrium bonding distances.Comment: 9 pages, 11 figure

kMap.py: A Python program for simulation and data analysis in photoemission tomography

For organic molecules adsorbed as well-oriented ultra-thin films on metallic surfaces, angle-resolved photoemission spectroscopy has evolved into a technique called photoemission tomography (PT). By approximating the final state of the photoemitted electron as a free electron, PT uses the angular dependence of the photocurrent, a so-called momentum map or k-map, and interprets it as the Fourier transform of the initial state's molecular orbital, thereby gains insights into the geometric and electronic structure of organic/metal interfaces. In this contribution, we present kMap.py which is a Python program that enables the user, via a PyQt-based graphical user interface, to simulate photoemission momentum maps of molecular orbitals and to perform a one-to-one comparison between simulation and experiment. Based on the plane wave approximation for the final state, simulated momentum maps are computed numerically from a fast Fourier transform of real space molecular orbital distributions, which are used as program input and taken from density functional calculations. The program allows the user to vary a number of simulation parameters such as the final state kinetic energy, the molecular orientation or the polarization state of the incident light field. Moreover, also experimental photoemission data can be loaded into the program enabling a direct visual comparison as well as an automatic optimization procedure to determine structural parameters of the molecules or weights of molecular orbitals contributions. With an increasing number of experimental groups employing photoemission tomography to study adsorbate layers, we expect kMap.py to serve as an ideal analysis software to further extend the applicability of PT

The Lyman Alpha Reference Sample: III. Properties of the Neutral ISM from GBT and VLA Observations

We present new H I imaging and spectroscopy of the 14 UV-selected star-forming galaxies in the Lyman Alpha Reference Sample (LARS), aimed for a detailed study of the processes governing the production, propagation, and escape of Ly$\alpha$ photons. New H I spectroscopy, obtained with the 100m Green Bank Telescope (GBT), robustly detects the H I spectral line in 11 of the 14 observed LARS galaxies (although the profiles of two of the galaxies are likely confused by other sources within the GBT beam); the three highest redshift galaxies are not detected at our current sensitivity limits. The GBT profiles are used to derive fundamental H I line properties of the LARS galaxies. We also present new pilot H I spectral line imaging of 5 of the LARS galaxies obtained with the Karl G. Jansky Very Large Array (VLA). This imaging localizes the H I gas and provides a measurement of the total H I mass in each galaxy. In one system, LARS 03 (UGC 8335 or Arp 238), VLA observations reveal an enormous tidal structure that extends over 160 kpc from the main interacting systems and that contains $>$10$^9$ M$_{\odot}$ of H I. We compare various H I properties with global Ly$\alpha$ quantities derived from HST measurements. The measurements of the Ly$\alpha$ escape fraction are coupled with the new direct measurements of H I mass and significantly disturbed H I velocities. Our robustly detected sample reveals that both total H I mass and linewidth are tentatively correlated with key Ly$\alpha$ tracers. Further, on global scales, these data support a complex coupling between Ly$\alpha$ propagation and the H I properties of the surrounding medium.Comment: Preprint form, 16 figures, accepted in Ap