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Full-Text Articles in Chemistry
The Golden Pathway To Thiolate-Stabilized Nanoparticles: Following The Formation Of Gold (I) Thiolate From Gold (Iii) Chloride, Brian M. Barngrover, Christine M. Aikens
The Golden Pathway To Thiolate-Stabilized Nanoparticles: Following The Formation Of Gold (I) Thiolate From Gold (Iii) Chloride, Brian M. Barngrover, Christine M. Aikens
Faculty Publications
Pathways for the formation of gold thiolate complexes from gold(III) chloride precursors AuCl4– and AuCl3 are examined. This work demonstrates that two distinct reaction pathways are possible; which pathway is accessible in a given reaction may depend on factors such as the residue group R on the incoming thiol. Density functional theory calculations using the BP86 functional and a polarized triple-ζ basis set show that the pathway resulting in gold(III) reduction is favored for R = methyl. A two-to-one ratio of thiol or thiolate to gold can reduce Au(III) to Au(I), and a three-to-one ratio can lead …
Incremental Binding Energies Of Gold (I) And Silver (I) Thiolate Clusters, Brian M. Barngrover, Christine M. Aikens
Incremental Binding Energies Of Gold (I) And Silver (I) Thiolate Clusters, Brian M. Barngrover, Christine M. Aikens
Faculty Publications
Density functional theory is used to find incremental fragmentation energy, overall dissociation energy, and average monomer fragmentation energy of cyclic gold(I) thiolate clusters and anionic chain structures of gold(I) and silver(I) thiolate clusters as a measure of the relative stability of these systems. Two different functionals, BP86 and PBE, and two different basis sets, TZP and QZ4P, are employed. Anionic chains are examined with various residue groups including hydrogen, methyl, and phenyl. Hydrogen and methyl are shown to have approximately the same binding energy, which is higher than phenyl. Gold–thiolate clusters are bound more strongly than corresponding silver clusters. Lastly, …