Zhang Wei, Kong Jie, Li Yingwei, Kuang Zhuoran, Wang He, Zhou Meng
Hefei National Research Center for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China Hefei Anhui 230026 China
Department of Chemistry and Chemical Biology, Harvard University 12 Oxford Street Cambridge Massachusetts 02138 USA.
Chem Sci. 2022 Jun 17;13(27):8124-8130. doi: 10.1039/d2sc02246j. eCollection 2022 Jul 13.
The coherent vibrational dynamics of gold nanoclusters (NCs) provides important information on the coupling between vibrations and electrons as well as their mechanical properties, which is critical for understanding the evolution from a metallic state to a molecular state with diminishing size. Coherent vibrations have been widely explored in small-sized atomically precise gold NCs, while it remains a challenge to observe them in large-sized gold NCs. In this work, we report the coherent vibrational dynamics of atomically precise Au(SR) NCs temperature-dependent femtosecond transient absorption (TA) spectroscopy. The population dynamics of Au(SR) consists of three relaxation processes: internal conversion, core-shell charge transfer and relaxation to the ground state. After removing the population dynamics from the TA kinetics, fast Fourier transform analysis on the residual oscillation reveals distinct vibrational modes at 1.5 THz (50 cm) and 2 THz (67 cm), which arise from the wavepacket motions along the ground-state and excited-state potential energy surfaces (PES), respectively. These results are helpful for understanding the physical properties of gold nanostructures with a threshold size that lies in between those of molecular-like NCs and metallic-state nanoparticles.
金纳米团簇(NCs)的相干振动动力学提供了关于振动与电子之间耦合及其力学性质的重要信息,这对于理解随着尺寸减小从金属态到分子态的演化至关重要。相干振动已在小尺寸原子精确的金纳米团簇中得到广泛研究,而在大尺寸金纳米团簇中观察到它们仍然是一个挑战。在这项工作中,我们通过温度相关的飞秒瞬态吸收(TA)光谱报告了原子精确的Au(SR)纳米团簇的相干振动动力学。Au(SR)的布居动力学由三个弛豫过程组成:内转换、核壳电荷转移和弛豫到基态。从TA动力学中去除布居动力学后,对残余振荡的快速傅里叶变换分析揭示了分别在1.5太赫兹(50厘米)和2太赫兹(67厘米)处的不同振动模式,它们分别源于沿基态和激发态势能面(PES)的波包运动。这些结果有助于理解具有介于类分子纳米团簇和金属态纳米颗粒之间阈值尺寸的金纳米结构的物理性质。
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