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

Electronic structures of chemically synthesized silver-based clusters [XAg(TBBT)] (X = Ag or Au; TBBT = 4--butylbenzenethiolate) having an icosahedral X@Ag 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.

Electron Affinities of Ligated Icosahedral M Superatoms Revisited by Gas-Phase Anion Photoelectron Spectroscopy.

The electron binding energies of the ligand-protected gold/silver-based cluster anions, [Au(SR)], [XAg(SR')] (X = Ag, Au, Pd, or Pt), and [PdAu(C≡CR″)] having icosahedral M superatomic cores, were reexamined by gas-phase photoelectron spectroscopy (PES) on a significantly intensified mass-selected ion beam. Laser fluence-dependent PE spectra and pump-probe PES revealed that the previous PE spectra were contaminated by PE signals due to the two-photon electron detachment via long-lived photoexcited states. Although the adiabatic electron affinities (AEAs) of the corresponding oxidized forms were found to be 1-2 eV larger than those previously reported, the effects of doping and ligation were not qualitatively affected.

Electron Binding in a Superatom with a Repulsive Coulomb Barrier: The Case of [Ag(SCHF)] in the Gas Phase.

The electron binding mechanism in [Ag(SCHF)] (SCHF = 3,4-difluorobenzenethiolate) tetra-anion was studied by photoelectron spectroscopy (PES), collision-induced dissociation mass spectrometry (CID-MS), and density functional theory (DFT) computations. PES showed that [Ag(SCHF)] is energetically metastable with respect to electron autodetachment {[Ag(SCHF)] + e} and features a repulsive Coulomb barrier (RCB) with a height of 2.7 eV.

Elucidating the Doping Effect on the Electronic Structure of Thiolate-Protected Silver Superatoms by Photoelectron Spectroscopy.

Gas-phase photoelectron spectroscopy (PES) was conducted on [XAg (SPhMe ) ] (X=Ag, Au) and [YAg (SPhMe ) ] (Y=Pd, Pt), which have a formal superatomic core (X@Ag ) or (Y@Ag ) with icosahedral symmetry. PES results show that superatomic orbitals in the (Au@Ag ) core remain unshifted with respect to those in the (Ag@Ag ) core, whereas the orbitals in the (Y@Ag ) (Y = Pd, Pt) core shift up in energy by about 1.4 eV.