Revisiting the structural and electronic properties of neutral, mono‐ and di‐anionic titanium‐doped silicon clusters TiSi_n^0/−/2− (n = 6‐16)

Abstract

The systematic structures search for neutral and Zintl anionic Ti-doped silicon clusters TiSi n 0/−/2− (n = 6-16) have been carried out using the ABCluster global search technique combined with a double-hybrid density functional method. Based on the predicted energies, adiabatic electron affinities, vertical detachment energies and the consistency between simulated and experimental photoelectron spectroscopy, the true global minimum structures are confirmed. The results show that structural growth pattern of neutral TiSi n clusters is from linked structures (n = 10-12) to encapsulated configurations (n = 13-16). In contrast, the evolution pattern of Zintl anionic TiSi n −/2− clusters begins with the pentagonal bipyramid structure (n = 6). As the Si atoms increase, these Si atoms attach to the surface adjacent to Ti atom, and gradually surround Ti atom. Eventually, the encapsulated structure is formed when n = 12. Moreover, two extra electrons not only perfect the structure of TiSi 12 but also improve its chemical and thermodynamic stability.adiabatic electron affinity, relative stability, simulated photoelectron spectroscopy, structural growth pattern of Ti-doped silicon clusters, vertical detachment energy

Structural evolution and electronic properties of neutral and anionic TiASil (A = Sc, Ti; l ≤ 12): relatively stable TiASi4 as a structural unit

“…58 Furthermore, the impossibility of completely determining the other structures on the potential surface is also well known. Fortunately, we employed an unprejudiced global optimization software, namely the ABCluster procedure 59,60 with excellent conjectures, to determine the valid isomers of multi-metal-silicon clusters 24,25,50 to predict the designs of the unknown structures in this study. The ABCluster procedure uses the ''artificial bee colony'' arithmetic to proceed efficiently with the global optimization.…”

“…Concurrently, numerous computational methods, including density functional theory (DFT), have been adopted to explore their structures and properties that can accurately predict target molecules mainly because of the complexities of selecting excited states, the consideration of the spin-orbit coupling, the strong relativistic effects, and the electron correlation. 23 The B3LYP functional, B3PW91 methods, CASSCF/CASPT2 methods, Perdew-Burke-Enzerhof (PBE) and mPW2PLYP/aug-cc-pVTZ schemes, 24,25 and ccCA-TM, G4, and G4(MP2) methods 26,27 were employed in previous study. For some time, researchers have theoretically and experimentally focused on the geometries and properties of single-metal-atom-doped silicon clusters.…”