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Structural, Energetics, and Electronic Properties Evolution of the 3d , 4d , and 5d Transition-Metal Clusters (30 TMn Systems for n = 2 − 15): A Density Functional Theory Investigation

Abstract

Subnanometric transition-metal (TM) clusters (smaller than 1 nm) have attracted great attention due to their unexpected physical and chemical properties, leastwise compared to their bulk counterparts. Besides, the unusual properties for gas-phase unary clusters can change further with size and charge state alterations. Thus, an indepth understanding of the properties evolution in function of the number of atoms for subnanometric clusters is a basic prerequisite to leverage countless applications, from catalysis to magnetic storage, as well as, to answer fundamental questions related with the intrinsic stability of these systems. However, the current understanding is not yet satisfactory, and a methodical study for all TM clusters is lacking in the literature. Here, we reported a systematic density functional study within the generalized gradient approximation to investigate the structural and electronic properties of the 2 up to 15-atom TM clusters, including all transitional metal elements, i.e., a total of 30 metals in the periodic table. We provided the complete structural patterns for all TM periodic table groups, considering the growth evolution, and the full picture for the structural geometries, as well as, the main trends of the structural and electronic properties. The combination between the occupation of the bonding/antibonding d-states and the s−d hybridization is found as the main stabilization mechanism, helping in the understanding of the structural patterns. Beyond that, most TM clusters have a magic number of atoms, for which there are peaks in s−d hybridization and null electric dipole moments. The same specific magic numbers occur for all elements in the same group, with few exceptions, which highlights the importance of the free-atom properties in this size regime, such as the number of valence electrons, the electronic occupation of atoms, and the promotion energy of their s and d valence orbitals. Our extensive and comparative study addresses size effects together with the evolution of d-orbital occupation for TM gas-phase cluster properties, which comprises one of the most complete theoretical studies in the gas-phase transition-metal clusters research.

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Publication details

The article was received on 07 Apr 2017, accepted on 18 May 2017 and first published on 18 May 2017


Article type: Paper
DOI: 10.1039/C7CP02240A
Citation: Phys. Chem. Chem. Phys., 2017, Accepted Manuscript
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    Structural, Energetics, and Electronic Properties Evolution of the 3d , 4d , and 5d Transition-Metal Clusters (30 TMn Systems for n = 2 − 15): A Density Functional Theory Investigation

    A. S. Chaves, M. J. Piotrowski and J. L. F. Da Silva, Phys. Chem. Chem. Phys., 2017, Accepted Manuscript , DOI: 10.1039/C7CP02240A

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