An Experimental and Theoretical Study of d10 Mixed Metal Nanoclusters in Alkali Halide Hosts

Heterometallic and homometallic nanoclusters of [Ag(CN)2]- and [Au(CN)2]- doped in NaCI, KCI, and NaBr exhibit multiple interesting photophysical phenomenon that are related to the variety of sizes, orientations, and compositions these clusters adapt. Samples of various dopant-host systems have been grown and analyzed with luminescence and Raman spectroscopy. In order to predict what cluster structures occur in these different systems, an atomistic surface model has been developed that probes the energetics of these clusters as they first form at surface kink sites. An order of preference in mixed-metal systems for heterometallic cluster formation over homometallic cluster formation, NaBr > NaCI > KCI, is predicted which agrees with findings on heterometallic cluster peaks in the luminescence spectra. Also, most tested predictions on homometallic cluster size, orientation, and structure selectivity for the single-metal systems correlate well with luminescence and Raman spectra. Structural orientations are predicted to be very different in heterometallic clusters as opposed to homometallic clusters.