Accurate non-adiabatic couplings from optimally tuned range-separated hybrid functionals

Precise theoretical calculations of non-adiabatic couplings, which describe the interaction between two Born-Oppenheimer surfaces, are important for the modeling of radiationless decay mechanisms in photochemical processes. Here, we demonstrate that accurate non-adiabatic couplings can be calculated in the framework of linear-response time-dependent density functional theory by using non-empirical, optimally tuned range-separated hybrid (OT-RSH) functionals. We focus on molecular radicals, in which ultrafast non-radiative decay plays a crucial role, to find that the OT-RSH functional compares well to wave-function-based reference data and competes with the accuracy of semi-empirical CAM-B3LYP calculations. Our findings show that the OT-RSH approach yields very accurate non-adiabatic couplings and, therefore, provides a computationally efficient alternative to wave-function-based techniques. (C) 2022 Author(s).

Automated summary

Accurate non-adiabatic couplings can be calculated using the optimally tuned range-separated hybrid functionals within the framework of linear-response time-dependent density functional theory, providing an efficient alternative to wave-function-based techniques in the modeling of radiationless decay mechanisms in photochemical processes.