Probing the stability of neutral and anionic transition-metal-doped golden cage nanoclusters: M@Au₁₆(M = Sc, Ti, V)

Abstract

The golden Au16(q) (q = 0, -1) cage is doped systematically with an external atom of different valence electrons: Sc, Ti, and V. The structural, electronic, and magnetic properties of the doped clusters, M@Au16(q) (M = Sc, Ti and V; q = 0, -1) are investigated using the Saunders "Kick" (SK) global search technique combined with density-functional theory (DFT) calculations (SK-DFT). It is found that the closeness of the calculated vertical/adiabatic detachment energy for Ti-doped and V-doped (3.09/3.16 eV for Ti-doped, and 3.31/3.38 eV for V-doped) is consistent with the negligible geometry change between the anionic and neutral ground state structures. The characteristics of the Sc@Au16(-) cluster includes its remarkably high average binding energy and doping energy, which reflects its high stability. The different spectral features between doped M@Au16(-) and pure Au16(-) clusters indicate endohedral structures with larger distortion from the parent Au16(-) cage for the doped clusters. The s electrons of the Au16 cage are observed to transfer to Sc, Ti and V atom for doped M@Au16(q) clusters by natural population analysis (NPA). The magnetic moment of the impurity Sc/Ti/V atom is somewhat quenched. Furthermore, the electron localization function analysis does not reveal strong interactions. The current work shows that the electronic properties of the golden cage can be systematically tuned through doping.

Vertical‐Resolved Composition and Aggregation Gradient of Conjugated‐Polymer@Insulator‐Matrix for Transistors and Memory

“…Water contact angle is used to identify the surface free energy of the substrates (bare SiO 2 and PTS modified SiO 2 ), the films of PS, conjugated‐polymers, and conjugated‐polymer@PS (95%) blends, which is an account for the tendency of phase separation in thermodynamics. [ 20,21 ] As shown in Figure S15 (Supporting Information), the water contact angles of these conjugated‐polymer films (≥100°) are generally larger than that of PS film (84°). This means these conjugated‐polymer films have lower surface free energy, which drives conjugated polymer to aggregate at the air‐surface during solvent evaporation, while PS with larger surface free energy is more compatible to the substrate.…”

“…[ 1,6,7,18,19 ] However, the phase separation of these two components during solvent evaporation should be carefully controlled, upon considering the complicated physical/chemical properties, such as solvent evaporation rate, solubility, and the crystallinity of polymers, as well as the interactions among conjugated polymer, insulator‐polymer, solvent and substrate. [ 20–22 ] While currently the phase evolution mechanism is still not fully understood, developing new approaches to optimize phase evolution of conjugated‐polymer/insulator‐matrix blends in the light of potentially newly revealed mechanism will be highly appreciated.…”

Stabilization of golden cages by encapsulation of a single transition metal atom

“…It is somewhat surprising that anionic structure A is 0.042 eV above the planar structure B at PBEPBE/SDD+2 f level of theory; however, calculated first ADE and VDE of structure A are in accord with experimental PES data [18,27] and better than those of structure B (ADE/VDE, theoretical: 3.89/4.02 eV for A, 3.75/3.78 eV for B; experimental: 3.99 ± 0.03/4.03 ± 0.03 eV, table 1). Our recent study [23] found that the global minimum structure A of Au 16 − cluster with C 2 symmetry is (about 0.10 eV) more stable than the planar structure B at PBEPBE/LANL2DZ level. To clearly compare simulated PES with the experimental PES, we present RMSD for the structures A and B, the smallest RMSD value (0.06 eV) for isomer A implies the closest match to experimental PES (table 1).…”

“…Up to now, Au 16 cluster and golden cage Au 16 doping with impurity atoms of 3d transition metal and alkali metal have attracted the attention of researchers in both theoretical and experimental studies devoting themselves to working in cluster science [16,18–23]. In a recent study, we have provided the first theoretical evidence of endohedral doping of the golden cages by the early 4d transition metals Y, Zr and Nb in Au 16 − cage [24].…”

Exploration of the Structural, Electronic and Tunable Magnetic Properties of Cu4M (M = Sc-Ni) Clusters

“…The binary alloy clusters have been investigated widely during the past several decades [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 ]. Experimental and theoretical research has manifested that the introduction of a dopant atom into a small cluster can considerably change the nature of the host cluster.…”