Premium
Revisit of large‐gap Si 16 clusters encapsulating group‐IV metal atoms (Ti, Zr, Hf)
Author(s) -
Wu Xue,
Zhou Si,
Huang Xiaoming,
Chen Maodu,
Bruce King R.,
Zhao Jijun
Publication year - 2018
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25545
Subject(s) - density functional theory , ground state , degenerate energy levels , crystallography , group (periodic table) , metal , adiabatic process , ion , chemistry , materials science , atomic physics , computational chemistry , physics , thermodynamics , organic chemistry , quantum mechanics
Doped clusters by Si 16 cage encapsulating group‐IV metal atoms (M@Si 16 , M = Ti, Zr and Hf) are computationally investigated by both density functional theory (DFT) and high‐level CCSD(T) method. Their low‐energy structures are globally searched using a genetic algorithm based on DFT. The ground state structures of neutral and anionic M@Si 16 are determined by calculating the vertical and adiabatic detachment energies and comparing them with the experimental data. For neutral Ti@Si 16 , the Frank‐Kasper (FK) deltahedron with T d symmetry and distorted FK isomer with C 3 v symmetry are nearly degenerate as the ground state and may coexist in laboratory, while the distorted FK isomer is the most probable structure for Ti@Si 16 − anion. For neutral and anionic Zr@Si 16 and Hf@Si 16 clusters, the ground states at finite temperatures up to 300 K are the fullerene‐like D 4d bitruncated square trapezohedron. These theoretical results establish a more complete picture for the most stable structures of M@Si 16 clusters, which possess large gaps and may serve as building blocks for electronic and optoelectronic applications.