Cubic aromaticity in ligand-stabilized doped Au superatoms
López-Estrada, O., Selenius, E., Zuniga-Gutierrez, B., Malola, S., & Häkkinen, H. (2021). Cubic aromaticity in ligand-stabilized doped Au superatoms. Journal of Chemical Physics, 154(20), Article 204303. https://doi.org/10.1063/5.0050127
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The magnetic response of valence electrons in doped gold-based [M@Au8L8]q 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@Au8L8]0 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. ...
PublisherAmerican Institute of Physic
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Related funder(s)Academy of Finland
Funding program(s)Research costs of Academy Professor, AoF; Academy Programme, AoF
Additional information about fundingThis 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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