Orbital tomography: Deconvoluting photoemission spectra of organic molecules

Abstract

We study the interface of an organic monolayer with a metallic surface, i.e., PTCDA (3,4,9,10-perylene-tetracarboxylic-dianhydride) on Ag(110), by means of angle-resolved photoemission spectroscopy (ARPES) and ab initio electronic structure calculations. We present a tomographic method that uses the energy and momentum dependence of ARPES data to deconvolute spectra into individual orbital contributions beyond the limits of energy resolution. This provides an orbital-by-orbital characterization of large adsorbate systems without the need to invoke a sophisticated theory of photoemission, allowing us to directly estimate the effects of bonding on individual orbitals. Moreover, these experimental data serve as a most stringent test necessary for the further development of ab initio electronic structure theory.