Master of Science (MSc)
Faculty of Science
Dr. Ian Hamilton
Alkane thiols, RSH, are commonly used in aqueous solution to stabilize and prevent aggregation of gold clusters, Aun. Initially a RSH-Aun complex is formed and, subsequently, there is hydrogen atom transfer to form a RSAunH complex. We examine the rate of this reaction for small neutral gold clusters, with n=1-2 and short-chain thiols with R = H, CH3, and CH3CH2, using transition state theory. The comparison of DFT (with the functionals, BP86 and M06-2X), and MP2 was performed. A pseudopotential was employed to account for the large relativisitic effects exhibited by gold. Equilibrium geometries and vibrational frequencies of the RSH-Aun and RSAunH complexes were obtained, as well as thermo-chemical values for the transfer of a hydrogen atom from sulphur to gold. The activation energy and rate of hydrogen atom transfer was also determined.
Smith, Silvija C., "A Computational Study of Small Gold Clusters with H2S, Thiols, H2O, and Alcohols" (2014). Theses and Dissertations (Comprehensive). 1640.