Theory of the d10–d10 Closed‐Shell Attraction: 1. Dimers Near Equilibrium

We study the dependence of the aurophilic attraction (AuI–AuI) in perpendicular model systems of the type [(ClAuPH3)2] on the ab initio method, basis set and different pseudopotentials used, and on relativity. The effects of varying the „halogen”︁ (X = F, H, Cl, Me, Br, ‐C≡CH, I), the „phosphine”︁ (L = PH3, PMe3, ‐N≡CH) and the metal (M = Cu, Ag, Au) on the M–M′ interaction of the [(XML)2] dimer are also studied. The depth of the interaction potential increases with the softness of the group X. It decreases by 27% for M = Au, X = Cl and L = PH3 if relativistic effects are omitted at fixed geometry.