Electronic
Structure and Optical Properties of the
Intrinsically Chiral 16-Electron Superatom Complex [Au<sub>20</sub>(PP<sub>3</sub>)<sub>4</sub>]<sup>4+</sup>
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Abstract
The
recently solved crystal structure of the [Au<sub>20</sub>(PP<sub>3</sub>)<sub>4</sub>]Cl<sub>4</sub> cluster (PP<sub>3</sub>: tris(2-(diphenylphophino)ethyl)phosphine)
is examined using density functional theory (DFT). The Au<sub>20</sub> core of the cluster is intrinsically chiral by the arrangement of
the Au atoms. This is in contrast to the chirality of thiolate-protected
gold clusters, in which the protecting Au-thiolate units are arranged
in chiral patterns on achiral cores. We interpret the electronic structure
of the [Au<sub>20</sub>(PP<sub>3</sub>)<sub>4</sub>]Cl<sub>4</sub> cluster in terms of the superatom complex model. The 16-electron
cluster cannot be interpreted as a dimer of 8-electron clusters (which
are magic). Instead, a superatomic electron configuration of 1S<sup>2</sup> 1P<sup>6</sup> 1D<sup>6</sup> 2S<sup>2</sup> is found. The
2S band is strongly stabilized, and the 1D states are nondegenerate
with a large gap. Ligand protection of the (Au<sub>20</sub>)<sup>4+</sup> core leads to a significant increase of the HL-gap and thus stabilization.
We also tested a charge of +II, which would give rise to an 18-electron
superatom complex. Our results indicate that the 16-electron cluster
is indeed more stable. We also investigate the optical properties
of the cluster. The experimental absorption spectrum is well-reproduced
by time-dependent DFT. Prominent transitions are analyzed by time-dependent
density-functional perturbation theory. The intrinsic chirality of
the cluster is compared to that of Au<sub>38</sub>(SR)<sub>24</sub>. We observe that the chiral arrangement of the protecting Au-SR
units in Au<sub>38</sub>(SR)<sub>24</sub> has very strong influence
on the strength of the CD spectra, whereas phosphine protection in
the title compound does not