Triplet Excitation-Energy Transfer Couplings from Subsystem Time-Dependent Density-Functional Theory

Käfer S.; Niemeyer N.; Tölle J.; Neugebauer J.

Abstract

We present an implementation of triplet excitation-energy transfer (TEET) couplings based on subsystem-based time-dependent density-functional theory (sTDDFT). TEET couplings are systematically investigated by comparing “exact” and approximate variants of sTDDFT. We demonstrate that, while sTDDFT utilizing explicit approximate non-additive kinetic energy (NAKE) density functionals is well-suited for describing singlet EET processes, it is inadequate for characterizing TEET. However, we show that projection-based embedding (PbE)-based sTDDFT addresses the challenges faced by NAKE-sTDDFT and emerges as a promising method for accurately describing electronic couplings in TEET processes. We also introduce the mixed PbE-/NAKE-embedding procedure to investigate the TEET effects in solvated pairs of chromophores. This approach offers a good balance between accuracy and efficiency, enabling comprehensive studies of TEET processes in complex environments.