Modeling the electronic structure of organic materials: a solid-state physicist’s perspective

Abstract

Abstract Modeling the electronic and optical properties of organic semiconductors remains a challenge for theory, despite the remarkable progress achieved in the last three decades. The complexity of these systems, including structural (dis)order and the still debated doping mechanisms, has been engaging theorists with different background. Regardless of the common interest across the various communities active in this field, these efforts have not led so far to a truly interdisciplinary research. In the attempt to move further in this direction, we present our perspective as solid-state theorists for the study of molecular materials in different states of matter, ranging from gas-phase compounds to crystalline samples. Considering exemplary systems belonging to the well-known families of oligo-acenes and -thiophenes, we provide a quantitative description of electronic properties and optical excitations obtained with state-of-the-art first-principles methods such as density-functional theory and many-body perturbation theory. Simulating the systems as gas-phase molecules, clusters, and periodic lattices, we are able to identify short- and long-range effects in their electronic structure. While the latter are usually dominant in organic crystals, the former play an important role, too, especially in the case of donor/accepetor complexes. To mitigate the numerical complexity of fully atomistic calculations on organic crystals, we demonstrate the viability of implicit schemes to evaluate band gaps of molecules embedded in isotropic and even anisotropic environments, in quantitative agreement with experiments. In the context of doped organic semiconductors, we show how the crystalline packing enhances the favorable characteristics of these systems for opto-electronic applications. The counter-intuitive behavior predicted for their electronic and optical properties is deciphered with the aid of a tight-binding model, which represents a connection to the most common approaches to evaluate transport properties in these materials.