A Computational Study of Small Gold Clusters with H2S, Thiols, H2O, and Alcohols

Author

Silvija C. Smith, Wilfrid Laurier UniversityFollow

Document Type

Thesis

Degree Name

Master of Science (MSc)

Department

Chemistry

Faculty/School

Faculty of Science

First Advisor

Dr. Ian Hamilton

Advisor Role

Supervisor

Abstract

Alkane thiols, RSH, are commonly used in aqueous solution to stabilize and prevent aggregation of gold clusters, Au_n. Initially a RSH-Au_n complex is formed and, subsequently, there is hydrogen atom transfer to form a RSAu_nH 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-Au_n and RSAu_nH 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.

Recommended Citation

Smith, Silvija C., "A Computational Study of Small Gold Clusters with H2S, Thiols, H2O, and Alcohols" (2014). Theses and Dissertations (Comprehensive). 1640.
https://scholars.wlu.ca/etd/1640

Convocation Year

2014

Convocation Season

Spring