Interexcited State Photophysics I: Benchmarking Density Functionals for Computing Nonadiabatic Couplings and Internal Conversion Rate Constants

We present the first benchmarking study of non adiabatic matrix coupling elements (NACMEs) calculated using different density functionals. Using the S1 -> S0 transition in perylene solvated in toluene as a case study, we calculate the photophysical properties and corresponding rate constants for a variety of density functionals from each rung of Jacob's ladder. The singlet photoluminescence quantum yield (sPLQY) is taken as a measure of accuracy, measured experimentally here as 0.955. Important quantum chemical parameters such as geometries, absorption, emission, and adiabatic energies, NACMEs, Hessians, and transition dipole moments were calculated for each density functional basis set combination (data set) using density functional theory based multireference configuration interaction (DFT/MRCI) and compared to experiment where possible. We were able to derive simple relations between the TDDFT and DFT/MRCI photophysical properties; with semiempirical damping factors of 0.843 +/- 0.017 and 0.954 +/- 0.064 for TDDFT transition dipole moments and energies to DFT/MRCI level approximations, respectively. NACMEs were dominated by out-of-plane derivative components belonging to the center-most ring atoms with weaker contributions from perturbations along the transverse and longitudinal axes. Calculated theoretical spectra compared well to both experiment and literature, with fluorescence lifetimes between 7.1 and 12.5 ns, agreeing within a factor of 2 with experiment. Internal conversion (IC) rates were then calculated and were found to vary wildly between 106-1016 s-1 compared with an experimental rate of the order 107 s-1. Following further testing by mixing data sets, we found a strong dependence on the method used to obtain the Hessian. The 5 characterized data sets ranked in order of most promising are PBE0/def2-TZVP, omega B97XD/def2-TZVP, HCTH407/TZVP, PBE/TZVP, and PBE/def2TZVP.

Automated summary

This benchmarking study investigates non adiabatic matrix coupling elements (NACMEs) using different density functionals, with a focus on the photophysical properties of perylene in toluene. The study compares theoretical calculations with experimental results, deriving relations between TDDFT and DFT/MRCI properties and identifying the most promising data sets.