Observation of Vibronic-Coupling-Mediated Energy Transfer in Light-Harvesting Nanotubes Stabilized in a Solid-State Matrix.
Observation of Vibronic-Coupling-Mediated Energy Transfer in Light-Harvesting Nanotubes Stabilized in a Solid-State Matrix.
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DOI：
10.1021/acs.jpclett.8b02325
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发表时间：
2018-08
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通讯作者：
Rajal Pandya;Richard Y. S. Chen;Alexandre Cheminal;Tudor H. Thomas;Arya Thampi;Arelo O. A Tanoh;Johannes M. Richter;Ravichandran Shivanna;F. Deschler;C. Schnedermann;A. Rao
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作者：
Rajal Pandya;Richard Y. S. Chen;Alexandre Cheminal;Tudor H. Thomas;Arya Thampi;Arelo O. A Tanoh;Johannes M. Richter;Ravichandran Shivanna;F. Deschler;C. Schnedermann;A. Rao
超快振动光谱获得实时结构信息的能量传输在双壁光捕获纳米管在室温下，稳定在主机矩阵模仿天然光捕获系统的刚性支架。我们观察到在315 cm-1处的低频振动模式的证据，该振动模式将激子从纳米管的外壁转移到交叉点，通过该交叉点可以发生能量转移到内壁。此外，该模式在溶液相中不存在。重要的是，这种模式的相干性在能量转移时不会转移到内壁，并且只存在于外壁的激发态能量表面上，突出显示外壁和内壁之间没有发生完全的能量转移。隔离的各个壁的纳米管提供的证据表明，这种模式对应于超分子运动的纳米管。我们的研究结果强调了固态环境在分子捕光系统中调制电子振动耦合和引导能量转移的重要性。
Ultrafast vibrational spectroscopy is employed to obtain real-time structural information on energy transport in double-walled light-harvesting nanotubes at room temperature, stabilized in a host matrix to mimic the rigid scaffolds of natural light-harvesting systems. We observe evidence of a low-frequency vibrational mode at 315 cm-1, which transfers excitons from the outer wall of the nanotubes to a crossing point through which energy transfer to the inner wall can occur. This mode is furthermore absent in solution phase. Importantly, the coherence of this mode is not transferred to the inner wall upon energy transfer and is only present on the outer wall's excited-state energy surface, highlighting that complete energy transfer between the outer and inner walls does not take place. Isolation of the individual walls of the nanotubes provides evidence that this mode corresponds to a supramolecular motion of the nanotubes. Our results emphasize the importance of the solid-state environment in modulating vibronic coupling and directing energy transfer in molecular light-harvesting systems.