Greatly Enhanced Electron Affinities of Au(2n)Cl Clusters (n = 1–4): Effects of Chlorine Doping

[Image: see text] Au(2n)Cl(–) (n = 1–4) clusters are investigated by both laser ablation mass spectrometry and theoretical calculations. It is interesting to find that the electron affinities of neutral Au(2n)Cl (n = 1–4) clusters are much larger than those of corresponding pure Au(2n) clusters. Among them, the electron affinity of Au(2)Cl is 4.02 eV, which can be defined as a very unique superhalogen that is quite different from classical ones of M(n)X(m) (M = metal, X = halogen, and n < m). Natural bond orbital and highest occupied molecular orbital analyses indicate that the extra electron is predominantly delocalized over the positively charged metal moiety in these anionic Au(2n)Cl(–) clusters, which is the main reason for the large electron affinities of the corresponding neutral species.