Structure-property relationships on thiolate-protected gold nanoclusters.

Since their discovery, thiolate-protected gold nanoclusters (Au n (SR) m ) have garnered a lot of interest due to their fascinating properties and "magic-number" stability. However, models describing the thermodynamic stability and electronic properties of these nanostructures as a function of their size are missing in the literature. Herein, we employ first principles calculations to rationalize the stability of fifteen experimentally determined gold nanoclusters in conjunction with a recently developed thermodynamic stability theory on small Au nanoclusters (≤102 Au atoms). Our results demonstrate that the thermodynamic stability theory can capture the stability of large, atomically precise nanoclusters, Au 279 (SR) 84 , Au 246 (SR) 80 , and Au 146 (SR) 57 , suggesting its applicability over larger cluster size regimes than its original development. Importantly, we develop structure-property relationships on Au nanoclusters, connecting their ionization potential and electron affinity to the number of gold atoms within the nanocluster. Altogether, a computational scheme is described that can aid experimental efforts towards a property-specific, targeted synthesis of gold nanoclusters.