Charge Localization in Acene Crystals from Ab Initio Electronic Structure

J Phys Chem Lett. 2023 Apr 6;14(13):3343-3351. doi: 10.1021/acs.jpclett.3c00191. Epub 2023 Mar 30.

Abstract

The performance of Koopmans-compliant hybrid functionals in reproducing the electronic structure of organic crystals is tested for a series of acene crystals. The calculated band gaps are found to be consistent with those achieved with the GW method at a fraction of the computational cost and in excellent accord with the experimental results at room temperature, when including the thermal renormalization. The energetics of excess holes and electrons reveals a struggle between polaronic localization and band-like delocalization. The consequences of these results on the transport properties of acene crystals are discussed.