The chemical reactivity of anionic species is strongly dependent on the electron affinity (EA) values of their corresponding neutral counterparts. Systems possessing anomalously large EA values (larger than that of chlorine) have been predicted and are termed as �superhalogens�. Superhalogens play an important role in a wide variety of areas, such as building blocks of high energy density materials, oxidizing agents, nucleating centers of aerosols in the atmosphere, and bio-catalysis. In view of their applications in such wide areas there is growing interest in the design and synthesis of new superhalogens. Recent anion photoelectron spectroscopic experiments have shown that AumOn (m = 2 � 4; n = 1 � 4) clusters exhibit superhalogen behavior. A traditional superhalogen typically consists of a central metal atom surrounded by halogen atoms. Therefore, AumOn nanoclusters are not conventional superhalogens. The experimental observation, thus, raises an important question: Why are AumOnclusters behaving as superhalogens?In this presentation we present our recent results obtained by carrying out a systematic computational investigation to understand the origin of the superhalogen behavior of AumOn nanoclusters. Using density functional theory (DFT) computations, we have studied the electronic structure and stabilities of neutral and negatively charged AumOn nanoclusters. The calculated EAs and electronic structure are in good agreement with the experimental results. Further analysis of Natural Bond Order (NBO) charges reveals the unusually high EA to be attributed to the delocalization of extra electron over the Aum part of the cluster.

Origin of the superhalogen properties of Au<sub>m</sub>O<sub>n</sub> nanoclusters

247th National Meeting (2014)

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Origin of the superhalogen properties of AumOn nanoclusters

Origin of the superhalogen properties of Au_mO_n nanoclusters