Stable Geometric and Electronic Structures of Gold-Coated Nanoparticles M@Au₁₂ (M = 5d Transition Metals, from Hf to Hg): I_h or O_h?

Abstract

The geometric and electronic structures of 5d transition metal “impurities” Hf to Hg encapsulated in icosahedral and cuboctahedral Au12 cages have been investigated theoretically. The best density functional results of the small molecules Au2, AuH, AuCl, and AuCu were obtained for the geometric structures with Xα, and for the electronic energies of those frozen structures with VBP. The same procedure was then applied to the clusters. At the zeroth order regular relativistic approximation ZORA, both at the spin-averaged scalar and at the spin−orbit-split spinor levels, the cuboctahedral clusters tend to be more stable than their icosahedral isomers, except for W@Au12. The neutral clusters have electronic closed shells only for I h and O h W@Au12 and for O h Hg@Au12. The embedding energy of M into Au12 is less attractive for the later transition metal atoms M.

Laser ablation synthesis of new gold phosphides using red phosphorus and nanogold as precursors. Laser desorption ionisation time‐of‐flight mass spectrometry

“…It is interesting to note that the gold cluster Au 12 is known to have a cage‐like shape and thus we suppose that the structure of Au 12 P n + ( n = 1, 2, 4) might be an endohedral type, i.e. gold‐covered phosphorus P n @Au 12 ( n = 1, 2, 4) clusters; but the structure of P n ‐Au 12 cluster‐cluster associates cannot be excluded.…”

“…An interesting structure of gold phosphide is that proposed by Sevillano et al [42] Several polyphosphide compounds have also been synthesised [43] and a theoretical study of bonding in the ternary gold polyphosphides, Au 2 MP 2 with M = Pb, Tl, or Hg, has shown that the crystal structure contains structural motifs of heterocyclic Au 2 P 6 and Au 4 P 6 'units' forming parallel channels which are filled by Pb, Tl or Hg atoms. 14 It is interesting to note that the gold cluster Au 12 is known to have a cage-like shape [44][45][46] and thus we suppose that the structure of Au 12 P n + (n = 1, 2, 4) might be an endohedral type, i.e. gold-covered phosphorus P n @Au 12 (n = 1, 2, 4) clusters; but the structure of P n -Au 12 cluster-cluster associates cannot be excluded.…”

Structures and Stabilities of the Metal Doped Gold Nano-Clusters: M@Au10 (M = W, Mo, Ru, Co)

“…Zhai et al [23] investigated M@Au 12 − (M = V, Nb, Ta), and Qiu et al [25] reported M@Au 12 (M = W, Pt, Au, Hg). Long et al studied the geometric and electronic structures of endohedral M@Au 12 (M = 5 d transition metals, from Hf to Hg) [26]. Very recently, Wang et al [27] investigated structural and photoelectron spectroscopic properties of the anionic Cu@Au 16 − and Cu@Au 17 − clusters both theoretically and experimentally.…”

Geometries, Stabilities and Electronic Properties of Au₁₂M (M=Na, Mg, Al, Si, P, S, Cl) Clusters

“…A novel Au20 tetrahedral structure identified by photoelectron spectroscopy correlates with relativistic density functional theory (DFT) calculations. 2 Fa and Dong 3 identified a stable tube-like Aun (n= [26][27][28] cluster with scalar, relativistic, all-electron DFT. Highly stable"golden fullerene"Au32 and Au42 clusters have been reported, 4,5 and core-shell structures have been verified by recent studies on Au34 and Au58 clusters.…”

“…[13][14][15] Since Pykko 16 and Li 17 et al first reported the existence of highly stable Au12W via photoelectron spectroscopy, a considerable amount of experimental and theoretical work has been carried out on Au clusters doped with other impurity atoms. 11,[18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] Most of these studies have focused on Au12 doped with transition-metal (TM) atoms. The high Ih or Oh symmetry of the lowest-energy Au12TM clusters is attributed to the strong relativistic effect, aurophilic attraction, and 18-electron bonding to the 4s, 5s, and 6s shells of the central heteroatom.…”