The shape of Au8: gold leaf or gold nugget?

Abstract

The size at which nonplanar isomers of neutral, pristine gold nanoclusters become energetically favored over planar ones is still debated amongst theoreticians and experimentalists. Spectroscopy confirms planarity is preferred at sizes up to Au7, however, starting with Au8, the uncertainty remains for larger nanoclusters. Au8 computational studies have had different outcomes: the planar D4h "cloverleaf" isomer competes with the nonplanar Td, C2v and D2d "nugget" isomers for greatest energetic stability. We here examine the 2D vs. 3D preference in Au8 by presenting our own B2PLYP, MP2 and CCSD(T) calculations on these isomers: these methods afford a better treatment of long-range correlation, which is at the root of gold's characteristic aurophilicity. We then use findings from these high-accuracy computations to evaluate two less expensive DFT approaches, applicable to much larger nanoclusters: alongside the standard functional PBE, we consider M06-L (highly parametrized to incorporate long-range dispersive interactions). We find that increasing basis set size within the B2PLYP framework has a greater destabilizing effect on the nuggets than it has on the Au8 cloverleaf. Our CCSD(T) and B2PLYP predictions, replicated by DFT-PBE, all identify the cloverleaf as the most stable isomer; MP2 and DFT-M06-L show overestimation of aurophilicity, and favor, respectively, the nonplanar D2d and Td nuggets in its stead. We conclude that PBE, which more closely reproduces CCSD(T) findings, may be a better candidate density functional for the simulation of gold nanoclusters in this context.