title: Evolution from the plasmon to exciton state in ligand-protected atomically precise gold nanoparticles.
abstract: The evolution from the metallic (or plasmonic) to molecular state in metal nanoparticles constitutes a central question in nanoscience research because of its importance in revealing the origin of metallic bonding and offering fundamental insights into the birth of surface plasmon resonance. Previous research has not been able to probe the transition due to the unavailability of atomically precise nanoparticles in the 1-3 nm size regime. Herein, we investigate the transition by performing ultrafast spectroscopic studies on atomically precise thiolate-protected Au25, Au38, Au144, Au333, Au∼520and Au∼940nanoparticles. Our results clearly map out three distinct states: metallic (size larger than Au333, that is, larger than 2.3 nm), transition regime (between Au333and Au144, that is, 2.3-1.7 nm) and non-metallic or excitonic state (smaller than Au144, that is, smaller than 1.7 nm). The transition also impacts the catalytic properties as demonstrated in both carbon monoxide oxidation and electrocatalytic oxidation of alcohol.
authors: Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA.
authors: Meng
authors: M
authors: Zhou
authors: Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA.
authors: Chenjie
authors: C
authors: Zeng
authors: Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA.
authors: Yuxiang
authors: Y
authors: Chen
authors: Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA.
authors: Shuo
authors: S
authors: Zhao
authors: Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, USA.
authors: Matthew Y
authors: MY
authors: Sfeir
authors: Department of Chemistry and Center for Atomic Engineering of Advanced Materials, Anhui University, Hefei, Anhui 230601, China.
authors: Manzhou
authors: M
authors: Zhu
authors: Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA.
authors: Rongchao
authors: R
authors: Jin