Refined standards for simulating UV-Vis absorption spectra of acceptors in organic solar cells by TD-DFT

Abstract Photoexcitation property of acceptor plays a vital role to understand fundamental physical process of acceptor excitation in organic solar cells (OSCs), which should be described at a reliable level and characterized by ultraviolet-visible (UV-Vis) absorption spectra. Generally, adiabatic linear-response time-dependent density functional theory (LR-TD-DFT) as a suitable framework, which requires to select exchange correlation functionals (XCFs) and basis sets to concentrate the approximation of models, is widely recognized. However, selecting reliable theoretical methods tends to consume computational cost and time, and optimal selections have not yet reached general standards. Herein, a systematic investigation including XCF, basis set, calculation density, solvation effect, and full width at half maximum (FWHM) was undertaken to quantify the photoexcitation properties of typical fullerene acceptors (FAs) and non-fullerene acceptors (NFAs). The results reveal that maximum absorption wavelength (λmax) of NFAs is strongly correlated with the fraction of “exact” Hartree-Fock exchange (EEX), thus establishing selection standards. Moreover, calculation density is the primary factor to ensure the integrity of spectra. This work provides reasonable schemes for characterization conditions, which further lays foundation for the reliability of theoretical calculations that will help to advance the theoretical characterization of optical properties of organic materials.