Institute for Physical and Theoretical Chemistry, Goethe University Frankfurt, 60438 Frankfurt, Germany; email:
Annu Rev Phys Chem. 2021 Apr 20;72:591-616. doi: 10.1146/annurev-physchem-090419-040306. Epub 2021 Feb 26.
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.
由于电子耦合、激子离域、非绝热效应和振子耦合等因素的微妙相互作用，需要进行量子动力学研究来阐明有机多色团体系中超快光诱导能量和电荷转移事件的细节。在这方面，我们综述了一种结合了基于第一性原理的参数化晶格哈密顿量和使用先进多组态方法进行精确量子动力学模拟的方法。我们重点关注有机功能材料中的基本转移步骤，研究了同聚物中的相干激子迁移和电荷转移激子的生成，特别是代表性的聚(3-己基噻吩)材料，以及聚合物：富勒烯异质结中的激子解离。我们强调了相干转移、高频声子模式引起的俘获效应以及低频软模引起的热激活在驱动扩散动力学中的作用。
