Low-Energy Charge-Transfer Excitons in Organic Solids from First-Principles: The Case of Pentacene

Abstract

The nature of low energy optical excitations, or excitons, in organic solids is of central relevance to many optoelectronic applications, including solar energy conversion. Excitons in solid pentacene, a prototypical organic semiconductor, have been the subject of many experimental and theoretical studies, with differing conclusions as to the degree of their charge-transfer character. Using first-principles calculations based on density functional theory and many-body perturbation theory, we compute the average electron–hole distance and quantify the degree of charge-transfer character within optical excitations in solid-state pentacene. We show that several low-energy singlet excitations are characterized by a weak overlap between electron and hole and an average electron–hole distance greater than 6 Å. Additionally, we show that the character of the lowest-lying singlet and triplet excitons is well-described with a simple analytic envelope function of the electron–hole distance.