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Physical Sciences and Mathematics Commons

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Chemistry

Stephen F. Austin State University

Faculty Publications

2011

Density functional theory

Articles 1 - 2 of 2

Full-Text Articles in Physical Sciences and Mathematics

Incremental Binding Energies Of Gold (I) And Silver (I) Thiolate Clusters, Brian M. Barngrover, Christine M. Aikens Jan 2011

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, …


Electron And Hydride Addition To Gold (I) Thiolate Oligomers: Implications For Gold–Thiolate Nanoparticle Growth Mechanisms, Brian M. Barngrover, Christine M. Aikens Jan 2011

Electron And Hydride Addition To Gold (I) Thiolate Oligomers: Implications For Gold–Thiolate Nanoparticle Growth Mechanisms, Brian M. Barngrover, Christine M. Aikens

Faculty Publications

Electron and hydride addition to Au(I):SR oligomers is investigated using density functional theory. Cyclic and chain-like clusters are examined in this work. Dissociation to Au ions and Aun(SR)n+1 chains is observed after 2–4 electrons are added to these systems. The free thiolate (SR) is rarely produced in this work; dissociation of Au is preferred over dissociation of SR. Electron affinities calculated in gas phase, toluene, and water suggest that the electron addition process is unlikely, although it may be possible in polar solvents. In contrast, hydride addition to Au(I):SR …