Density-functional global optimization of gold nanoclusters

The structure of gas-phase gold clusters of size $\ensuremath{\sim}20$ is studied by density-functional global optimization in the full configuration space. The putative global minimum of ${\mathrm{Au}}_{20}$ is confirmed to be a tetrahedron $({T}_{d})$ independently of the choice of the exchange-correlation functional, whereas the structure of the low-lying excited states depends on the theoretical approach. The peculiar stability of ${T}_{d}$ is rationalized in terms of the synergic effects of $s\text{\ensuremath{-}}d$ hybridization and electronic shell closure. Calculations on ${\mathrm{Au}}_{16}$ and ${\mathrm{Au}}_{18}$ show that ${T}_{d}$ ${\mathrm{Au}}_{20}$ possibly represents a ``unicum'' in the sequence of gold clusters.

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