Quasiparticle and optical spectroscopy of the organic semiconductors pentacene and PTCDA from first principles

The broad use of organic semiconductors for optoelectronic applications relies on quantitative understanding and control of their spectroscopic properties. Of paramount importance are the transport gap-the difference between ionization potential and electron affinity-and the exciton binding energy-inferred from the difference between the transport and optical absorption gaps. Transport gaps are commonly established via photoemission and inverse photoemission spectroscopy (PES/IPES). However, PES and IPES are surface-sensitive, average over a dynamic lattice, and are subject to extrinsic effects, leading to significant uncertainty in gaps. Here, we use density functional theory and many-body perturbation theory to calculate the spectroscopic properties of two prototypical organic semiconductors, pentacene, and 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA), quantitatively comparing with measured PES, IPES, and optical absorption spectra. For bulk pentacene and PTCDA, the computed transport gaps are 2.4 and 3.0 eV, and optical gaps are 1.7 and 2.1 eV, respectively. Computed bulk quasiparticle spectra are in excellent agreement with surface-sensitive photoemission measurements over several eV only if the measured gap is reduced by 0.6 eV for pentacene and 0.6-0.9 eV for PTCDA. We attribute this redshift to several physical effects, including incomplete charge screening at the surface, static and dynamical disorder, and experimental resolution. Optical gaps are in excellent agreement with experiment with solid-state exciton binding energies of ∼0.5 eV for both systems; for pentacene the exciton is delocalized over several molecules and exhibits significant charge transfer character. Our parameter-free calculations provide new interpretation of spectroscopic properties of organic semiconductors critical to optoelectronics.