Triplet Excitation-Energy Transfer Couplings from Subsystem Time-Dependent Density-Functional Theory
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 Excitation-Energy Transfer (SEET) 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 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.
Keywords
Cite
@article{arxiv.2312.07123,
title = {Triplet Excitation-Energy Transfer Couplings from Subsystem Time-Dependent Density-Functional Theory},
author = {Sabine Käfer and Niklas Niemeyer and Johannes Tölle and Johannes Neugebauer},
journal= {arXiv preprint arXiv:2312.07123},
year = {2023}
}