Collision-Induced Fission of Oblate Gold Superatom in [Au₉(PPh₃)₈]³⁺: Deformation-Mediated Mechanism

Abstract

+ (Au3)) upon sufficiently high energy collision, associated with splitting the number of valence electrons in the superatomic orbitals from 6e (Au9) into 4e (Au6) and 2e (Au3). Density functional theory calculations revealed oblate and prolate cores of Au9 and Au6 with semiclosed superatomic electron configurations of (1S) 2 (1P x ) 2 (1P y ) 2 and (1S) 2 (1P z ) 2 , respectively. This result indicated a significant deformation of the cluster-core motif during the CID process. We attribute the clear difference between PdAu8 and Au9 to the softer Au−Au bond in Au9 and propose that the collision-induced structural deformation plays a critical role in the fission.

Revisiting ultrasmall phosphine-stabilized rhodium-doped gold clusters AunRh (n = 5, 6, 7, 8): geometric, electronic, and vibrational properties

“…39 Both the structures of Au 8 Rh and the butterfly isomer of Au 9 are toroidal rather than spherical in shape such as in the case of the crown isomer of Au 9 and Au 8 Pd. 38–40 This difference in the bonding pattern causes the 1p z orbital to be higher in energy, making it unavailable for skeletal bonding and subsequently deviating from the expected MO trend based on electron count. Additionally, the contribution of δ orbitals from Rh stabilizes the LUMO+1 (1p z ) orbital of Au 8 Rh.…”

Beyond Shell-Filling: Strong Enhancement of Electron Affinity of Metal Clusters through a Noninvasive Oriented External Electric Field

“…Atomic clusters, as stable aggregates that connect individual atoms with bulk materials, combine several to thousands of atoms or ions through robust physical or chemical interactions. − These clusters exhibit a distinct set of characteristics, including critical features such as quantum size effects, , the stabilizing influence of magic numbers, , and the synergistic interaction between electron shell structures and energy bands. , These properties remain highly pertinent across various applied scientific fields. Significantly, the emergence of the cluster concept introduces a unique perspective, propelling atomic clusters to a prominent status that challenges the traditional atom-focused approach. − …”