Optical spectra from molecules to crystals: Insight from many-body perturbation theory

Abstract

Time-dependent density-functional theory (TDDFT) often successfully reproduces excitation energies of finite systems, already in the adiabatic local-density approximation (ALDA). Here we show for prototypical molecular materials, i.e., oligothiophenes, that ALDA largely fails and explain why this is so. By comparing TDDFT with an in-depth analysis based on many-body perturbation theory, we demonstrate that correlation effects crucially impact energies and character of the optical excitations not only for molecules of increasing length and in crystalline environment, but even for isolated small molecules. We argue that only high-level methodologies, which explicitly include correlation effects, can reproduce optical spectra of molecular materials with equal accuracy from gas phase to crystal structures.