Local Phonon Environment as a Design Element for Long-Lived Excitonic Coherence: Dithia-anthracenophane Revisited

Abstract

The purpose of this study is to investigate the role of a structured immediate phonon environment in determining the exciton dynamics and the possibility of using it as an optimal design element. Through the case study of dithia-anthracenophane, a bichromophore using the Hierarchical Equations Of Motion formalism, we show that the experimentally observed coherent exciton dynamics can be reproduced only by considering the actual structure of the phonon environment. While the slow dephasing of quantum coherence in dithia-anthracenophane can be attributed to strong vibronic coupling to high-frequency modes, vibronic quenching is the source of long oscillation periods in population transfer. This study sheds light on the crucial role of the structure of the immediate phonon environment in determining the exciton dynamics. We conclude by proposing some design principles for sustaining long-lived coherence in molecular systems.