Wenbo Sun, Tammo van der Heide, Van-Quan Vuong, Thomas Frauenheim, Michael A. Sentef, Bálint Aradi, & Carlos R. Lien-Medrano

J. Chem. Theory Comput.  (2025)

Density functional tight binding (DFTB) is a quantum chemical simulation method based on an approximate density functional theory (DFT), known for its low computational cost and comparable accuracy to DFT. For several years, the application of DFTB in organic photovoltaics (OPV) has been limited by the absence of an appropriate set of parameters that adequately account for the relevant elements and necessary corrections. Here we have developed new parametrizations using hybrid functionals, including B3LYP and CAM-B3LYP, for OPV applications within the DFTB method in order to overcome the self-interaction error present in DFT functionals lacking long-range correction. These parametrizations encompass electronic and repulsive parameters for the elements H, C, N, O, F, S, and Cl. A Bayesian optimization approach was employed to optimize the free atom eigenenergies of unoccupied shells. The effectiveness of these new parametrizations was evaluated by a data set of 12 OPV donor and acceptor molecules, showing consistent performance when compared with their corresponding DFT references. Frontier molecular orbitals and optimized geometries were examined to evaluate the performance of the new parametrizations in predicting ground-state properties. Furthermore, the excited-state properties of monomers and dimers were investigated by means of real-time time-dependent DFTB (real-time TD-DFTB). The appearance of charge-transfer (CT) excitations in the dimers was observed, and the influence of alkyl side-chains on the photoinduced CT process was explored. This work paves the way for studying ground- and excited-state properties, including band alignments and CT mechanisms at donor–acceptor interfaces, in realistic OPV systems.