Issue 8, 2023

Effect of total charge on the electronic structure of thiolate-protected X@Ag12 superatoms (X = Ag, Au)

Abstract

Electronic structures of chemically synthesized silver-based clusters [XAg16(TBBT)12]3− (X = Ag or Au; TBBT = 4-tert-butylbenzenethiolate) having an icosahedral X@Ag12 superatomic core were studied by gas-phase photoelectron spectroscopy and density functional theory calculations. The electron binding energy of the highest occupied molecular orbital (HOMO) with a 1P superatomic nature was determined to be 0.23 and 0.29 eV for X = Ag or Au, respectively. Resonant tunnelling electron emission through the repulsive Coulomb barrier (RCB) was observed. From the kinetic energy of the tunnelling electrons, it was estimated that the lowest unoccupied molecular orbital (LUMO) was supported at 1.51 and 1.62 eV above the vacuum level by the RCB for X = Ag or Au, respectively. The HOMO of [XAg16(TBBT)12]3− (X = Ag or Au) was destabilized by 3.74 and 3.71 eV, respectively, compared with those of [XAg24(DMBT)18] (DMBT = 2,4-dimethylbenzenethiolate) having the icosahedral X@Ag12 core due to the larger negative charge imparted by the ligand layers.

Graphical abstract: Effect of total charge on the electronic structure of thiolate-protected X@Ag12 superatoms (X = Ag, Au)

Supplementary files

Article information

Article type
Paper
Submitted
29 Oct 2022
Accepted
05 Jan 2023
First published
06 Jan 2023
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2023,25, 5955-5959

Effect of total charge on the electronic structure of thiolate-protected X@Ag12 superatoms (X = Ag, Au)

K. Nakamura, S. Ito, K. Koyasu and T. Tsukuda, Phys. Chem. Chem. Phys., 2023, 25, 5955 DOI: 10.1039/D2CP05079J

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