Interexcited State Photophysics II: A Qualitative Excited State Dynamics Model from First-Principles

Abstract

In Part I of this series [J. Chem. Theory Comput. 2023, 19(1), 271-292], a benchmarking study of nuclear-electronic couplings was performed using 15 density functionals across two basis sets. From these, five density functional and basis set combinations (data sets) yielded results that agreed with experiments for the S1 → S0 internal conversion (IC) rate in perylene. In this Part II, we use those five data sets to calculate the excited state dynamics in perylene up to the second excited state within a density functional theory (DFT) framework. Interexcited state IC was found to be generally overestimated by 10 orders of magnitude at ∼1020 s-1 in the best case for the S2 → S1 pathway. Probin..