Intermolecular conical intersections in molecular aggregates
Intermolecular conical intersections in molecular aggregates
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DOI：
10.1038/s41565-020-00791-2
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发表时间：
2020-11-16
影响因子：
38.3
通讯作者：
Lienau, Christoph
中科院分区：
文献类型：
--
作者：
De Sio, Antonietta;Sommer, Ephraim;Lienau, Christoph
多维势能面的圆锥交叉点（CoIns）在自然界中普遍存在，并控制着许多光引发的分子内过程的途径和产率。此类拓扑结构可能参与聚集分子或聚合物中的能量传输，但尚未被发现。在这里，使用超快二维电子光谱（2DES），我们揭示了存在的分子间CoIns的分子聚集体相关的光致发光。超快，低于10 fs的2DES跟踪振动波包在光学亮态上的相干运动，并在仅40 fs后通过CoIn突然过渡到暗态。非绝热动力学模拟确定分子间CoIn作为这些不寻常的动力学的来源。我们的研究结果表明，分子间CoIns可以有效地引导光电子功能纳米结构中的能量路径。二维电子光谱揭示了分子间的锥形交叉点的存在与光电子相关的分子聚集体。
Conical intersections (CoIns) of multidimensional potential energy surfaces are ubiquitous in nature and control pathways and yields of many photo-initiated intramolecular processes. Such topologies can be potentially involved in the energy transport in aggregated molecules or polymers but are yet to be uncovered. Here, using ultrafast two-dimensional electronic spectroscopy (2DES), we reveal the existence of intermolecular CoIns in molecular aggregates relevant for photovoltaics. Ultrafast, sub-10-fs 2DES tracks the coherent motion of a vibrational wave packet on an optically bright state and its abrupt transition into a dark state via a CoIn after only 40 fs. Non-adiabatic dynamics simulations identify an intermolecular CoIn as the source of these unusual dynamics. Our results indicate that intermolecular CoIns may effectively steer energy pathways in functional nanostructures for optoelectronics.Two-dimensional electronic spectroscopy reveals the existence of intermolecular conical intersections in molecular aggregates relevant for photovoltaics.