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

Abstract

Abstract We study the dependence of the aurophilic attraction (Au I –Au I ) in perpendicular model systems of the type [(ClAuPH 3 ) 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 = PH 3 , PMe 3 , ‐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 = PH 3 if relativistic effects are omitted at fixed geometry.