Author : Silvija C. Smith
Publisher :
ISBN 13 :
Total Pages : 288 pages
Book Rating : 4.:/5 (96 download)
Book Synopsis A Computational Study of Small Gold Clusters H2S, Thiols, H2O, and Alcohols by : Silvija C. Smith
Download or read book A Computational Study of Small Gold Clusters H2S, Thiols, H2O, and Alcohols written by Silvija C. Smith and published by . This book was released on 2014 with total page 288 pages. Available in PDF, EPUB and Kindle. Book excerpt: Bulk gold is known to be one of the least reactive metals. In contrast, gold colloids and gold nanoclusters exhibit unique chemical and physical properties, due to their stability, uniformity, and size related characteristics. These interesting attributes cause gold nanoclusters to have promising applications in catalysis, biosensors, and optoelectronics. In particular, many of the applications for gold nanoclusters are in the fields of biomedicine and biotechnology. These potential applications require aggregation resistant, water-soluble nanoparticles capable of withstanding an environment within living organisms. Additionally, previous studies have shown that supported gold nanoclusters can be used as catalysts for many hydrogenation and oxidation reactions at low temperatures. These reactions include the oxidation of carbon monoxide (CO) and nitric oxide (NO), partial oxidation of propylene, and partial and complete hydrogenation of acetylene and ethylene, respectively. In this thesis, density functional theory (DFT) calculations are used to obtain energies of equilibrium structures from geometry optimizations and vibrational frequencies of small gold clusters, with one to four gold atoms bonded to a water molecule, small alcohols, or short-chain thiols, SHR, wth R=H, CH 3, CH3 CH2 . Additionally, density functional theory, Moller-Plesset Perturbation theory, and coupled cluster theory calculations were used to obtain energies, optimal geometries, vibrational frequencies, activation energies, and the rate of reaction for the hydrogen atom transfer from sulphur to gold of the RSH-Au n and RSAun H complexes. These complexes consist of small gold clusters, with n=1-4 and short-chain thiols wth R=H, CH3, and CH3 CH2. The Gibbs free energies were calculated to determine whether the hydrogen atom transfer occurs as a thermodynamically spontaneous reaction. Additionally, common trends of the cluster complexes including bond lengths and characteristic gold-sulphur and gold-oxygen vibrational stretching were examined. Depending on the ligand attached to the gold cluster and the overall charge of the complex, bridge-bonding to different pairs of gold atoms in the cluster can occur with the hydrogen atom that has been transferred and the sulphur atom or oxygen atom. These theoretical studies are used to expand on the limited understanding of gold clusters and their interesting characteristics. Additionally, these studies determine the versatility of various basis functionals and basis sets when used on many electron atoms, such as gold. The results from this study are compared to similar studies involving gold clusters.
