Quantum dynamical studies of ultrafast charge separation in nanostructured organic polymer materials: Effects of vibronic interactions and molecular packing
Quantum dynamical studies of ultrafast charge separation in nanostructured organic polymer materials: Effects of vibronic interactions and molecular packing
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DOI：
10.1002/qua.25502
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发表时间：
2018-01
影响因子：
2.2
通讯作者：
Matthias A. Polkehn;P. Eisenbrandt;H. Tamura;I. Burghardt
中科院分区：
文献类型：
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作者：
Matthias A. Polkehn;P. Eisenbrandt;H. Tamura;I. Burghardt
我们回顾了最近的工作，采用高维量子动力学技术来研究功能有机材料中的超快电荷分离，在了解的关键微观因素，导致高效的电荷产生在光致发光应用。正如最近的实验所强调的那样，这些过程可以由量子相干性指导，尽管存在静态和动态无序。本方法结合了第一原理参数化晶格哈密顿，时间依赖密度泛函理论（TDDFT）和/或高层次的电子结构计算的基础上，精确的量子动力学模拟使用多配置时间依赖哈特里（MCTDH）方法。这一贡献具体解决了（i）区域规则的寡聚噻吩-富勒烯聚集体，和（ii）高度有序的寡聚噻吩-二萘嵌苯二酰亚胺共聚低聚物组件中的电荷产生机制。这些研究强调，供体-受体组合的化学设计需要考虑电子离域的影响和由于分子堆积而改变的能量学，以及由电子振动相互作用引起的多个转移途径和内部转换通道。
We review recent work employing high-dimensional quantum dynamical techniques to study ultrafast charge separation in functional organic materials, in view of understanding the key microscopic factors that lead to efficient charge generation in photovoltaics applications. As highlighted by recent experiments, these processes can be guided by quantum coherence, despite the presence of static and dynamic disorder. The present approach combines first-principles parametrized lattice Hamiltonians, based on Time-Dependent Density Functional Theory (TDDFT) and/or high-level electronic structure calculations, with accurate quantum dynamics simulations using the Multi-Configuration Time-Dependent Hartree (MCTDH) method. This contribution specifically addresses the mechanism of charge generation in (i) regioregular oligothiophene-fullerene aggregates, and (ii) highly ordered oligothiophene-perylene diimide co-oligomer assemblies. These studies highlight that chemical design of donor–acceptor combinations needs to account for the effects of electronic delocalization and the modified energetics due to molecular packing, as well as multiple transfer pathways and internal conversion channels induced by vibronic interactions.