Communication: Determining the lowest-energy isomer of Au8: 2D, or not 2D

A parallel numerical derivative code, combined with parallel implementation of the coupled-cluster method with singles, doubles, and non-iterative triples (CCSD(T)), is used to optimize the geometries of the low-energy structures of the Au8 particle. The effects of geometry relaxation at the CCSD(T) level and the combined effects of the basis set and core-valence correlations are examined and the results are compared with the corresponding second-order Møller-Plesset perturbation theory calculations. The highest-level computations, in which the single-point CCSD(T) calculations employing the correlation-consistent basis set of the cc-pVTZ quality and the associated relativistic effective core potential (ECP), both optimized for gold, and correlating the 5d(10)6s(1) valence and 5s(2)5p(6) semi-core electrons, are combined with the geometrical information obtained with the corresponding CCSD(T)/cc-pVDZ/ECP approach, favor the planar configuration, with the next three non-planar structures separated by 4-6 kcal/mol. In agreement with the earlier work, smaller-basis set CCSD(T) computations provide unreliable results for the relative energetics, even when the geometries are optimized at the CCSD(T) level.