Zhang Baicheng, Gu Yonghao, Freixas Victor Manuel, Sun Shichao, Tretiak Sergei, Jiang Jun, Mukamel Shaul
Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China.
Department of Chemistry and Department of Physics and Astronomy, University of California, Irvine, Irvine, California 92697-2025, United States.
J Am Chem Soc. 2024 Oct 2;146(39):26743-26750. doi: 10.1021/jacs.4c06727. Epub 2024 Sep 18.
Dendrimers are branched polymers with wide applications to photosensitization, photocatalysis, photodynamic therapy, photovoltaic conversion, and light sensor amplification. The primary step of numerous photophysical and photochemical processes in many molecules involves ultrafast coherent electronic dynamics and charge oscillations triggered by photoexcitation. This electronic wavepacket motion at short times where the nuclei are frozen is known as attosecond charge migration. We show how charge migration in a dendrimer can be manipulated by placing it in an optical cavity and monitored by time-resolved X-ray diffraction. Our simulations demonstrate that the dendrimer charge migration modes and the character of photoexcited wave function can be significantly influenced by the strong light-matter interaction in the cavity. This presents a new avenue for modulating initial ultrafast charge dynamics and subsequently controlling coherent energy transfer in dendritic nanostructures.
树枝状聚合物是一种支化聚合物，在光敏化、光催化、光动力疗法、光伏转换和光传感器放大等方面有广泛应用。许多分子中众多光物理和光化学过程的首要步骤涉及由光激发引发的超快相干电子动力学和电荷振荡。在原子核冻结的短时间内的这种电子波包运动被称为阿秒电荷迁移。我们展示了如何通过将树枝状聚合物置于光学腔中来操纵其电荷迁移，并通过时间分辨X射线衍射进行监测。我们的模拟表明，腔内强光 - 物质相互作用可显著影响树枝状聚合物的电荷迁移模式和光激发波函数的特性。这为调节初始超快电荷动力学以及随后控制树枝状纳米结构中的相干能量转移提供了一条新途径。
