title: Electronic structure of thiolate-covered gold nanoparticles: Au102(MBA)44.
abstract: We present first principles, density functional theory (DFT) calculations of the structural and electronic properties of thiolate-protected gold nanoparticles [Au(102)(MBA)(44) ] that have been recently crystallized and measured by X-ray diffraction. Our calculations yield structural properties in very good agreement with experiment and reveal the impact of thiolate adsorption on both the surface geometry and the electronic structure of the gold core; in particular, within DFT we observe the emergence of an energy gap of about 0.5 eV, upon MBA adsorption. Using a localized orbital analysis, we characterize the electron distribution in the nanoparticle and provide insight into the bonding of thiolates on curved gold surfaces.
authors.affiliation: Department of Chemistry, University of California, Davis, California 95616, USA. ynli@ucdavis.edu
authors.forename: Yan
authors.initials: Y
authors.lastname: Li
authors.forename: Giulia
authors.initials: G
authors.lastname: Galli
authors.forename: François
authors.initials: F
authors.lastname: Gygi
mesh_terms: D003198:Computer Simulation; D003460:Crystallization / Q000379:methods; D004553:Electric Conductivity; D004583:Electrons; D006046:Gold / Q000737:chemistry*; D046911:Macromolecular Substances / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D049329:Nanostructures / Q000737:chemistry* / Q000648:ultrastructure*; D036103:Nanotechnology / Q000379:methods*; D010316:Particle Size; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013499:Surface Properties
chemical_list: D046911:Macromolecular Substances; D013438:Sulfhydryl Compounds; D006046:Gold