Prediction of Excited-State Properties of Oligoacene Crystals Using Fragment-Based Quantum Mechanical Method

A fundamental understanding of the excited-state properties of molecular crystals is of central importance for their optoelectronics applications. In this study, we developed the electrostatically embedded generalized molecular fractionation (EE-GMF) method for the quantitative characterization of the excited-state properties of locally excited molecular clusters. The accuracy of the EE-GMF method is systematically assessed for oligoacene crystals. Our result demonstrates that the EE-GMF method is capable of providing the lowest vertical singlet (S₁) and triplet excitation energies (T₁), in excellent agreement with the full-system quantum mechanical calculations. Using this method, we also investigated the performance of different density functionals in predicting the excited-state properties of the oligoacene crystals. Among the 13 tested functionals, B3LYP and MN15 give the two lowest overall mean unsigned errors with reference to the experimental S₁ and T₁ excitation energies. The EE-GMF approach can be readily utilized for studying the excited-state properties of large-scale organic solids at diverse ab initio levels.