Interplay between Magnetism and Magicness in Nanoclusters

Our experimental and theoretical investigation focuses on the role of magnetism on the structures and energetics of nanoclusters of the important 3d antiferromagnetic (AFM) semiconductor, manganese sulphide (MnS). Our cluster beam mass spectra for both (MnS) n and (MnSe) n show a pronounced “magic” abundance, at n = 13, in accord with results for other nonmagnetic chalcogenide clusters (e.g., CdS, CdSe, ZnS, ZnSe). Using global optimization and ab initio calculations we focus on cluster isomers of (MnS)13 and its two neighboring compositions, (MnS)12 and (MnS)14, and show that the magic status of the former is fully compatible with the high relative energetic stability of the n = 13 ground state with respect to those for n ± 1. We demonstrate a strong symbiosis between cluster structure and spin ordering, which leads to a particular type of AFM spin-ordered ground-state cluster structure being energetically selected for all cluster sizes and which enhances the magic stability of (MnS)13. This nanomagnetostructural effect highlights a fundamental link between magnetism and cluster structure having potential implications for (nano)technologies based on magnetostructural transitions (e.g., data storage, magnetic refrigeration).