X-ray absorption study of platinum and palladium atoms in argon matrices: Evidence for platinum in a substitutional site and a short Pd[sbnd]Ar interaction

Abstract

The Pt L3-edge X-ray absorption spectrum of Pt atoms generated in a hollow cathode sputtering device and trapped in an Ar matrix yielded a PtAr distance of 3.78(4) Å with a coordination number of ca. 12 which confirms the evidence from electronic absorption spectroscopy that Pt atoms occupy a substitutional site in the Ar lattice. These data also yield a van der Waals radius for Pt atoms of 1.90 Å. The Pd K-edge X-ray absorption spectrum of sputtered Pd atoms trapped in an Ar matrix is radically different to that for Pt atoms. The analysis reveals a much shorter PdAr distance of 2.53(3) Å with a low coordination number close to 1, together with an “atomic” EXAFS like spectrum with no significant oscillations indicating the absence of any well defined nearest neighbours. On annealing to 25 K, the 2.53(3) Å interaction essentially disappears to leave the “atomic” spectrum. The featureless “atomic” spectrum is associated with Pd 1S0 atoms in an argon substitutional site, or other site such as a grain boundary with high disorder. The short PdAr distance of 2.53(3) Å is consistent with Pd atoms with a 1S0 atomic ground state in an interstitial octahedral site, the formation of a PdArn exciplex with a short PdAr distance, or the formation of a more formal palladium argon compound such as PdAr2. Although it is not possible to be definitive, the most likely carrier of the short PdAr distance is a PdArn exciplex. What is clear is that this work has identified a short PdAr interaction for the first time.