Point Group Symmetry Analysis of the Electronic Structure of Bare and Protected Metal Nanocrystals
Kaappa, S., Malola, S., & Häkkinen, H. (2018). Point Group Symmetry Analysis of the Electronic Structure of Bare and Protected Metal Nanocrystals. Journal of Physical Chemistry A, 122(43), 8576-8584. https://doi.org/10.1021/acs.jpca.8b07923
Published inJournal of Physical Chemistry A
© 2018 American Chemical Society
The electronic structures of a variety of experimentally identified gold and silver nanoclusters from 20 to 246 atoms, either unprotected or protected by several types of ligands, are characterized by using point group specific symmetry analysis. The delocalized electron states around the HOMO-LUMO energy gap, originating from the metal s-electrons in the cluster core, show symmetry characteristics according to the point group that describes best the atomic arrangement of the core. This indicates strong effects of the lattice structure and overall shape of the metal core to the electronic structure, which cannot be captured by the conventional analysis based on identification of spherical angular momentum shells in the "superatom" model. The symmetry analysis discussed in this paper is free from any restrictions regarding shape or structure of the metal core, and is shown to be superior to the conventional spherical harmonics analysis for any symmetry that is lower than Ih. As an immediate application, we also demonstrate that it is possible to reach considerable savings in computational time by using the symmetry information inside a conventional linear-response calculation for the optical absorption spectrum of the Ag55 cluster anion, without any loss in accuracy of the computed spectrum. Our work demonstrates an efficient way to analyze the electronic structure of nonspherical, but atomically ordered nanocrystals and ligand-protected clusters with nanocrystal metal cores, and it can be viewed as the generalization of the superatom model demonstrated for spherical shapes 10 years ago (Walter, M.; et al. Proc. Natl. Acad. Sci. U. S. A. 2008, 105, 9157-9162). ...
PublisherAmerican Chemical Society
Publication in research information system
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Related funder(s)Academy of Finland
Funding program(s)Research costs of Academy Professor, AoF
Additional information about fundingThis research was supported by the Academy of Finland (Grant 294217 and H.H.’s Academy Professorship). The computational resources were provided by CSCthe Finnish IT Center for Science and by the Barcelona supercomputing center as part of the PRACE NANOMETALS project. We thank Zhikun Wu for discussions on the work in ref 32 prior to its publication. S.K. thanks Vilho, Yrjö, and Kalle Vaisälä̈ Foundation for a Ph.D. study grant. ...
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