Rh ₁₉ ⁻ : A high-spin super-octahedron cluster

Abstract

Probing atomic clusters with magic numbers is of supreme importance but challenging in cluster science. Pronounced stability of a metal cluster often arises from coincident geometric and electronic shell closures. However, transition metal clusters do not simply abide by this constraint. Here, we report the finding of a magic-number cluster Rh 19 − with prominent inertness in the sufficient gas-collision reactions. Photoelectron spectroscopy experiments and global-minimum structure search have determined the geometry of Rh 19 − to be a regular O h ‑[Rh@Rh 12 @Rh 6 ] − with unusual high-spin electronic configuration. The distinct stability of such a strongly magnetic cluster Rh 19 − consisting of a nonmagnetic element is fully unveiled on the basis of its unique bonding nature and superatomic states. The 1-nanometer–sized O h -Rh 19 − cluster corresponds to a fragment of the face-centered cubic lattice of bulk rhodium but with altered magnetism and electronic property. This cluster features exceptional electron-spin state isomers confirmed in photoelectron spectra and suggests potential applications in atomically precise manufacturing involving spintronics and quantum computing.

Synthesis and characterization of iron clusters with an icosahedral [Fe@Fe12]16+ Core

“…We also demonstrate that three β electrons of the W atom are involved in one Fe−W bond, leading to the oxidation state W(III) and the number of unpaired electrons for compound 2 to be 32. The special stability of this [Fe@Fe 12 ] cluster bears resemblance in superatom characteristics to the recently found Rh@Rh 12 @Rh 6 [ 48 ] and Co@Co 12 O 8 clusters with cubic aromaticity [ 4 ]. The synthesis and crystallization of this Fe 13 cluster underscores a feasible synthetic methodology toward reactive late transition-metal clusters with higher nuclearity.…”

Tailoring Titanium Carbide Clusters for New Materials: from Met-Cars to Carbon-Doped Superatoms

“…For these clusters, the orbitals located at lower energy (e.g., −20 eV for Ti 8 C 12 and −14 eV for Ti 14 C 13 ; Ti 17 C 2 and Ti 19 C 10 at −13 ∼ −14 eV) are dominantly contributed by the C­(2s) electrons, while the C­(2p) orbitals hybridize with Ti­(3 d /4s) at higher energy levels. The PDOS compositions of Ti 17 C 2 and Ti 19 C 10 exhibit comparable patterns, with many hybridized orbitals above −8 eV showing vivid superatomic features. , Notably, the superatomic 1S and 1P z orbitals of Ti 17 C 2 are mainly composed of the 2s orbitals of the carbon atoms, while the superatomic 1P x , 1P y , 2S, 2P, and 1D orbitals are caused by hybridization of the valence C­(2p) orbitals and Ti­(3 d /4s) orbitals. This is analogous but partly different from the superatomic feature of nascent Ti 17 (Figure S23).…”

Unusually High-Spin Fe12C12– Metallo-Carbohedrene Clusters

“…Notably, the Jahn−Teller effect leads to a plumb−bob structure for the lowest-energy isomer A, an ellipsoid structure for the homologous isomer B, a bulging cage structure for isomer D, and a slightly distorted cage for isomer C (with four C 1 units and four C 2 units). It is worth mentioning that all these isomers feature exceptional electron-spin state isomers (ESSIs) 45 of energy proximity, as partly shown in Figure 2b,c. Therefore, the broad PES hot bands produced by the 266 nm laser ionization can be understood within diverse electronic transitions from thermally populated ESSI levels of the Fe 12 C 12 − cluster to the corresponding neutral Fe 12 C 12 according to the PES selection rule.…”