Quantum Dynamics of Exciton Transport and Dissociation in Multichromophoric Systems

• Published in: Annual review of physical chemistry Vol. 72; no. 1; pp. 591 - 616
• Main Authors: Popp, Wjatscheslaw, Brey, Dominik, Binder, Robert, Burghardt, Irene
• Format: Journal Article
• Language: English
• Published: United States Annual Reviews 20.04.2021; Annual Reviews, Inc
• Subjects: Charge transfer; coherence; Couplings; electron-phonon coupling; excitation energy transfer; exciton dissociation; Excitons; First principles; Functional materials; Heterojunctions; Lattice vibration; organic functional materials; Polymers; quantum dynamics; vibronic effects; exciton dissociation; excitation energy transfer; coherence; electron-phonon coupling; quantum dynamics; excitons; organic functional materials; vibronic effects
• ISSN: 0066-426X; 1545-1593
• DOI: 10.1146/annurev-physchem-090419-040306

Due to the subtle interplay of site-to-site electronic couplings, exciton delocalization, nonadiabatic effects, and vibronic couplings, quantum dynamical studies are needed to elucidate the details of ultrafast photoinduced energy and charge transfer events in organic multichromophoric systems. In this vein, we review an approach that combines first-principles parameterized lattice Hamiltonians with accurate quantum dynamical simulations using advanced multiconfigurational methods. Focusing on the elementary transfer steps in organic functional materials, we address coherent exciton migration and creation of charge transfer excitons in homopolymers, notably representative of the poly(3-hexylthiophene) material, as well as exciton dissociation at polymer:fullerene heterojunctions. We emphasize the role of coherent transfer, trapping effects due to high-frequency phonon modes, and thermal activation due to low-frequency soft modes that drive a diffusive dynamics.