This theoretical investigation examines the formation of non radical Au(0) species from the reduction of Au(I) species. The Au(I) complexes of interest are AuCl2-, AuClPH3, and AuCl(H)SCH3(-), which are precursors for gold nanoparticle and cluster formation. Reaction of two of the Au(I) species with a hydride results in the ejection of two of the ligands and the formation of Au2 with two ligands still attached. The reaction energy for two AuCl2- in methanol is -1.34 eV and in benzene is -0.07 eV. AuClPH3 reactions can either eject chloride, HCl, or PH3. The reaction energy to form Au2(PH3)2 in methanol is -1.06 eV and the energy to form AuClPH3- is -0.73 eV. AuClHSCH3 reactions are similar to the phosphine reactions, where a chloride, HCl, or a thiol can be ejected. It is more favored to form Au2(HSCH3)2 than Au2ClHSCH3 with reaction energies of -1.36 eV and -1.21 eV. AuClSCH3 can also be used it has the option to eject chloride, HCl, thiol, or thiolate. The most favored reaction is the formation of Au2ClSCH32- with a thiol and a chloride with a reaction energy of -1.21 eV. The next favored reaction is the formation of  Au2(SCH3)22- with a reaction energy of -0.52 eV. The least favored reaction is Au2ClSCH32- and a thiolate and HCl formation with a reaction energy of 0.009 eV. The Au2Cl22- complex then can further react with the AuCl2- starting material, which forms Au3Cl32- and a chloride anion with a reaction energy in methanol of -0.57 eV and in benzene of -0.56 eV. The new Au3Cl32- species can further react with either of the initial structures or with another Au3Cl32-.  This is the first investigation to show how Au(0)-containing species can be formed without assuming the formation of Au(0) atoms (radical species).

Reduction of Au(I) species to Au(0)-containing species during gold nanoparticle growth and the effects of solvent

247th National Meeting (2014)

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