Coherent vibrational dynamics of Au₁₄₄(SR)₆₀ nanoclusters

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 Au₁₄₄(SR)₆₀ NCs via temperature-dependent femtosecond transient absorption (TA) spectroscopy. The population dynamics of Au₁₄₄(SR)₆₀ 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^-1) and 2 THz (67 cm^-1), 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.