Abstract

Golden cage-doped nanoclusters have attracted great attention in the past decade due to their remarkable electronic, optical and catalytic properties. However, the structures of large golden cage doped with Mo and Tc are still not well known because of the challenges in global structural searches. Here, we report anionic and neutral golden cage doped with a transition metal atom MAu16 (M = Mo and Tc) using Saunders ‘Kick' stochastic automation search method associated with density-functional theory (DFT) calculation (SK-DFT). The geometric structures and electronic properties of the doped clusters, MAu16q (M = Mo and Tc; q = 0 and −1), are investigated by means of DFT theoretical calculations. Our calculations confirm that the 4d transition metals Mo and Tc can be stably encapsulated in the Au16− cage, forming three different configurations, i.e. endohedral cages, planar structures and exohedral derivatives. The ground-state structures of endohedral cages C2v Mo@Au16−-(a) and C1 Tc@Au16−-(b) exhibit a marked stability, as judged by their high binding energy per atom (greater than 2.46 eV), doping energy (0.29 eV) as well as a large HOMO–LUMO gap (greater than 0.40 eV). The predicted photoelectron spectra should aid in future experimental characterization of MAu16− (M = Mo and Tc).

Highlights

  • Nanoclusters display many new properties, which are usually not found in their bulk counterparts [1,2,3]

  • We present a combined Saunders ‘Kick’ global search technique and density-functional theory study of anionic and neutral doped golden cage clusters MAu16 (M = Mo and Tc)

  • The global minimum search revealed that the endohedral cages represent the global minimum structure for the doped gold clusters MAu16q

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Summary

Introduction

Nanoclusters display many new properties, which are usually not found in their bulk counterparts [1,2,3]. These novel properties can be attributed almost to strong relativistic effects and finitesize quantum effects [4,5]. As the geometry of the cluster is closely related to its properties, an understanding of the cluster geometry is of primary interest.

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