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[Au 12 (SR) 6 ] 2− , As Smaller 8‐Electron Gold Nanocluster Retaining an SP 3 ‐Core. Evaluation of Bonding and Optical Properties from Relativistic DFT Calculations
Author(s) -
MuñozCastro Alvaro,
Saillard JeanYves
Publication year - 2018
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201800088
Subject(s) - superatom , nanoclusters , cluster (spacecraft) , electron , gold cluster , chirality (physics) , core (optical fiber) , chemistry , crystallography , chemical physics , nanostructure , electronic structure , materials science , molecular physics , nanotechnology , atomic physics , physics , computational chemistry , chiral symmetry breaking , quantum mechanics , quark , computer science , nambu–jona lasinio model , composite material , programming language
Abstract Exploring the versatility of atomically precise clusters is a relevant issue in the design of functional nanostructures. Superatomic clusters offer an ideal framework to gain further understanding of the different distinctive size‐dependent physical and chemical properties. Here, we propose [Au 12 (SR) 6 ] 2− as a minimal 8‐electron superatom related to the prototypical [Au 25 (SR) 18 ] − cluster, depicting half of its core‐mass (2.3 kDa vs 5.0 kDa). The [Au 12 (SMe) 6 ] 2− cluster fulfills a 1S 2 1P 6 electronic configuration, with a distorted tetrahedral Au 8 core further viewed as an SP 3 ‐hybridized superatom. The distinctive optical properties show a blue‐shift for the first relevant 1P→1D transition, in comparison to [Au 25 (SR) 18 ] − . In addition, chiroptical activity is observed, denoting intrinsic core chirality. We expect that our results can shed light into the variation of the molecular properties according to the size‐dependent properties, and serve as guidelines for further experimental exploration of minimal or ultrasmall nanoclusters.