Study on Structural Evolution, Thermochemistry and Electron Affinity of Neutral, Mono- and Di-Anionic Zirconium-Doped Silicon Clusters ZrSin0/-/2- (n = 6–16)

International Journal of Molecular Sciences

Limin Han¹  Caixia Dong¹  Jucai Yang¹  Lin Cheng¹ 

[1] Inner Mongolia Key Laboratory of Theoretical and Computational Chemistry Simulation, School of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051, China;

关键词: the most stable neutral and Zintl anionic Zr-doped silicon clusters;    structural evolution patterns;    simulated photoelectron spectroscopy;    stability;    HOMO-LUMO gap;   

DOI  :  10.3390/ijms20122933

来源: DOAJ

【 摘 要 】

We have carried out a global search of systematic isomers for the lowest energy of neutral and Zintl anionic Zr-doped Si clusters ZrSi_n^0/-/2- (n = 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_n clusters prefer the attaching type (n = 6−9) to the half-cage motif (n = 10−13), and finally to a Zr-encapsulated configuration with a Zr atom centered in a Si cage (n = 14−16). For Zintl mono- and di-anionic ZrSi_n^-/2-, their growth patterns adopt the attaching configuration (n = 6−11) to encapsulated shape (n = 12−16). The further analyses of stability and chemical bonding make it known that two extra electrons not only perfect the structure of ZrSi₁₅ but also improve its chemical and thermodynamic stability, making it the most suitable building block for novel multi-functional nanomaterials.

【 授权许可】

Unknown