Au279(SR)84: The Smallest Gold Thiolate Nanocrystal That Is Metallic and the Birth of Plasmon

We report a detailed study on the optical properties of Au-279(SR)(84) using steady-state and transient absorption measurements to probe its metallic nature, time dependent density functional theory (TDDFT) studies to correlate the optical spectra, and density of states (DOS) to reveal the factors governing the origin of the collective surface plasmon resonance (SPR) oscillation. Au-279 is the smallest identified gold nanocrystal to exhibit SPR. Its optical absorption exhibits SPR at 510 nm. Power dependent bleach recovery kinetics of Au-279 suggests that electron dynamics dominates its relaxation and it can support plasmon oscillations. Interestingly, TDDFT and DOS studies with different tail group residues (-CH3 and -Ph) revealed the important role played by the tail groups of ligands in collective oscillation. Also, steady-state and time resolved absorption for Au-36, Au-44, and Au-133 were studied to reveal the molecule-to-metal evolution of aromatic AuNMs. optical gap and transient decay lifetimes decrease as the size increases.