Discovery of a silicon-based ferrimagnetic wheel structure in V_xSi₁₂⁻ (x = 1–3) clusters: photoelectron spectroscopy and density functional theory investigation

Abstract

Our studies show that VSi(12)(-) adopts a V-centered hexagonal prism with a singlet spin state. The addition of the second V atom leads to a capped hexagonal antiprism for V(2)Si(12)(-) in a doublet spin state. Most interestingly, V(3)Si(12)(-) exhibits a ferrimagnetic, bicapped hexagonal antiprism wheel-like structure with a total spin of 4 μ(B).

Structural determination of niobium-doped silicon clusters by far-infrared spectroscopy and theory

“…[6][7][8][9][10][11][12] Different from carbon clusters that usually show sp 2 hybridization, bonding in pure silicon clusters occurs through sp 3 hybridization and thus they are more chemically reactive due to the existence of unsaturated dangling bonds on the clusters' surface, making them less suitable as nanoscale building blocks. 13 However, it has been found that silicon clusters can be stabilized by doping with transition metal (TM) atoms, [14][15][16] and by now a great number of studies, both experimentally [17][18][19][20][21][22][23][24][25][26][27][28][29] and theoretically, [30][31][32][33][34][35][36] have explored the structures and electronic properties of TM-doped silicon clusters for their potential use in silicon-based nanomaterials. In fact, doping silicon clusters with appropriate transition metal atoms [37][38][39][40][41] can reduce the number of dangling bonds on the cluster surface or even fully saturate them via pd hybridization, and thereby change the geometrical structures and chemical reactivities compared to pure silicon clusters.…”

Exploring the structural stability order and electronic properties of transition metal M@Ge12 (M = Co, Pd, Tc, and Zr) doped germanium cage clusters

“…The calculations to search low lying structures of M@Ge 12 (M = Co, Pd, Tc, and Zr) in this work began with lot of previous geometries where transition metal atom sits at various different position i.e. (1) Substitution (2) Endohedral (3) Exohedral on the basis of optimized Ge 12 and calculated at all possible spin states as reported in the literature [1][2][3][4][5][6][7][8][9][10] . All the initial geometries optimized without any symmetry constraint.…”

“…Electronic and structural properties of transition metal encapsulated in germanium clusters are incredibly dynamic area of exploration because of its significant in building block for clusters assembled materials and other expected applications in numerous fields [1][2][3][4][5][6][7][8][9][10] . Without a doubt, doping in silicon confine clusters has additionally stood out because of its applications in nanoelectronic gadgets and building blocks nanomaterials [7][8][9][10] .…”

The nature of structure and bonding between transition metal and mixed Si‐Ge tetramers: A 20‐electron superatom system

“…However, pure semiconductor clusters favor the sp 3 hybridization, and are chemically reactive due to the existence of unsaturated dangling bonds, resulting in the formation of unstable cage structures . Until now, it has been found that the doping of semiconductor clusters with proper transition metal (TM) atoms, can solve the deficiency, and largely enhance the chemical stability of the clusters, which depends on the cluster size and the TM dopant (e.g., with partially filled or filled d shell), while the fascinating physicochemical properties, such as large HOMO−LUMO gaps, high magnetic moments, bright photoluminescence, can be introduced for designing novel functional cluster‐assembled materials. Recently, the nonlinear optical properties of metal‐doped silicon clusters were explored using the conventional ab initio and density functional theory (DFT) methods, and it was revealed that the alkali‐metal doping can obviously enhance the hyperpolarizabilities of pure silicon clusters, with particular application in the realm of nonlinear optics .…”