The influence of passivating ligand on electron-phonon relaxation dynamics of the smallest sized gold clusters was studied using ultrafast transient absorption spectroscopy and theoretical modeling. The electron dynamics in Au279, Au329, and Au329 passivated with 4-tert-butylbenzene thiol (TBBT), phenylethane thiol (SC2Ph) and hexane thiol (SC6), respectively, were investigated. These clusters were chosen as they are the smallest gold clusters reported till-date to show plasmonic behavior. Ultrafast transient absorption measurements were also carried out on Au~1400 (SC6) and Au~2000 (SC6) to understand the influence of the size on electron-phonon relaxation with the same passivating ligand. The study has revealed interesting aspects on the role of ligand on electron-phonon relaxation dynamics wherein the aromatic passivating ligands, SC2Ph and TBBT, have shown smaller power dependence and higher plasmon bleach indicating dampened plasmon resonance while the cluster with aliphatic passivating ligand has behaved similarly to regular plasmonic gold nanoparticles. To model the effect of the ligand on the plasmonic properties of the investigated samples, free electron density correction factor of each one was calculated using three-layered Mie theory, and the results show that SC6 interacts least with core-gold while TBBT and SC2Ph have a greater effect on the surface electronic conductivity that is attributed to π-interaction of the ligand with gold. The results also shed light on unusual electron-phonon relaxation and smaller slope observed for Au329 (SC2Ph) that is ascribed to surface gold-π interaction creating a hybrid state. In contrast, extended π-interaction is probably the reason for plasmonic nature observed in Au279 (TBBT) even though its size is smaller when compared to Au329. In addition, the results also have shown that the electron-phonon coupling has increased with an increase in the size of the cluster and theoretical modeling has shown higher electron conductivity for larger plasmonic gold clusters.
|Publication status||Published - 2019 Feb 5|
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