| Summary: | We have carried out a global search of systematic isomers for the lowest energy of neutral and Zintl anionic Zr-doped Si clusters ZrSi<i><sub>n</sub></i><sup>0/-/2-</sup> (<i>n</i> = 6−16) by employing the ABCluster global search method combined with the mPW2PLYP double-hybrid density functional. In terms of the evaluated energies, adiabatic electron affinities, vertical detachment energies, and agreement between simulated and experimental photoelectron spectroscopy, the true global minimal structures are confirmed. The results reveal that structural evolution patterns for neutral ZrSi<i><sub>n</sub></i> clusters prefer the attaching type (<i>n</i> = 6−9) to the half-cage motif (<i>n</i> = 10−13), and finally to a Zr-encapsulated configuration with a Zr atom centered in a Si cage (<i>n</i> = 14−16). For Zintl mono- and di-anionic ZrSi<sub>n</sub><sup>-/2-</sup>, their growth patterns adopt the attaching configuration (<i>n</i> = 6−11) to encapsulated shape (<i>n</i> = 12−16). The further analyses of stability and chemical bonding make it known that two extra electrons not only perfect the structure of ZrSi<sub>15</sub> but also improve its chemical and thermodynamic stability, making it the most suitable building block for novel multi-functional nanomaterials.
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