Table 1.

Experimentally determined band gaps for free gas-phase gold cluster anions from photoelectron spectroscopy vs. theoretical DFT values (PBE functional) for HOMO–LUMO gaps of passivated gold cluster compounds that correspond to 8, 34, and 58 conduction-electron shell closings

Shell closingExperiment
Theory (this work)
ClusterGap, eVCluster compoundGap, eV
8e (1S21P6)Au11(PH3)7(SMe)3 1.5
8eAu11(PH3)7Cl3 2.1
8eAu13(PH3)10Cl2 3+ * 1.8
8eAu25(SMe)18 1.2
34e (8e + 1D102S21F14)Au34,§ 1.0Au39Cl6(PH3)14 0.8
58e (34e + 2P61G18)Au58, 0.6Au102(p-MBA)44 0.5
58eAu102(SMe)44 0.5
  • *Ref. 16; the cationic charge is compensated by 3 non-coordinated PF6 anions in the experimental crystal structure.

  • Ref. 41.

  • Ref. 32.

  • §Ref. 34.

  • Ref. 33.

  • The calculation of the optical gap by a single-pole approximation in linear-response time-dependent DFT yields 0.55 eV for compound 2.