Resolving Vibrational from Electronic Coherences in Two-Dimensional Electronic Spectroscopy: The Role of the Laser Spectrum
Resolving Vibrational from Electronic Coherences in Two-Dimensional Electronic Spectroscopy: The Role of the Laser Spectrum
复制标题
DOI：
10.1103/physrevlett.118.033001
复制
发表时间：
2017-01-20
影响因子：
8.6
通讯作者：
Heisler, Ismael A.
中科院分区：
文献类型：
--
作者：
Camargo, Franco V. de A.;Grimmelsmann, Lena;Heisler, Ismael A.
对光合作用捕光复合体中相干量子效应的观察引发了一个问题，即是否可以利用量子相干来提高新能源材料的效率。相干效应的详细描述依赖于敏感的方法，如二维电子光谱(2D-ES)。然而，由于复杂的分子结构中存在许多可能的偶联，2D-ES产生的结果的解释是具有挑战性的。在这项工作中，我们演示了激光光谱轮廓如何在单体生色团中诱导类电子相干信号，从而潜在地导致数据误解。我们认为激光光谱对某些相干路径起到了滤光片的作用，从而提出了区分振动相干和电子相干的一般方法。
The observation of coherent quantum effects in photosynthetic light-harvesting complexes prompted the question whether quantum coherence could be exploited to improve the efficiency in new energy materials. The detailed characterization of coherent effects relies on sensitive methods such as two-dimensional electronic spectroscopy (2D-ES). However, the interpretation of the results produced by 2D-ES is challenging due to the many possible couplings present in complex molecular structures. In this work, we demonstrate how the laser spectral profile can induce electronic coherencelike signals in monomeric chromophores, potentially leading to data misinterpretation. We argue that the laser spectrum acts as a filter for certain coherence pathways and thus propose a general method to differentiate vibrational from electronic coherences.