Cubic aromaticity in ligand-stabilized doped Au superatoms

Omar López-Estrada, Elli Selenius, Bernardo Zuniga-Gutierrez, Sami Malola, Hannu Häkkinen*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

4 Citations (Scopus)


The magnetic response of valence electrons in doped gold-based M@Au8L8q superatoms (M = Pd, Pt, Ag, Au, Cd, Hg, Ir, and Rh; L = PPh3; and q = 0, +1, +2) is studied by calculating the gauge including magnetically induced currents (GIMIC) in the framework of the auxiliary density functional theory. The studied systems include 24 different combinations of the dopant, total cluster charge, and cluster structure (cubic-like or oblate). The magnetically induced currents (both diatropic and paratropic) are shown to be sensitive to the atomic structure of clusters, the number of superatomic electrons, and the chemical nature of the dopant metal. Among the cubic-like structures, the strongest aromaticity is observed in Pd- and Pt-doped M@Au8L80 clusters. Interestingly, Pd- and Pt-doping increases the aromaticity as compared to a similar all-gold eight-electron system Au9L8+1. With the recent implementation of the GIMIC in the deMon2k code, we investigated the aromaticity in the cubic and butterfly-like M@Au8 core structures, doped with a single M atom from periods 5 and 6 of groups IX-XII. Surprisingly, the doping with Pd and Pt in the cubic structure increases the aromaticity compared to the pure Au case not only near the central atom but encompassing the whole metallic core, following the aromatic trend Pd > Pt > Au. These doped (Pd, Pt)@Au8 nanoclusters show a closed shell 1S21P6 superatom electronic structure corresponding to the cubic aromaticity rule 6n + 2.

Original languageEnglish
Article number204303
JournalJournal of Chemical Physics
Issue number20
Publication statusPublished - 28 May 2021

Bibliographical note

Funding Information:
This work was supported by the Academy of Finland (Grant Nos. 294217, 319208, and 315549) and through H.H. Academy Professorship. E.S. acknowledges the Finnish Cultural Foundation for a Ph.D. study grant. The computations were made at the Nanoscience Center of the University of Jyväskylä by utilizing the FCCI (Finnish Computing Competence Infrastructure, persistent indentifier urn:nbn:fi:research-infras-2016072533) and at the Barcelona Supercomputing Center as a PRACE project (Grant No. 2018194723). B.Z.-G. acknowledges the funding from CONACyT (Project No. CB-2015-258647).

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