DFT study of dissociative adsorption of sulfur compounds on Au(111)

P.G. LUSTEMBERG; P. N. ABUFAGER; M.L. MARTIARENA; C. CRESPOS; A.E. MARTÍNEZ; H. F. BUSNENGO

Reisensburg, Alemania

Workshop; Workshop “Non-Adiabatic Dynamics at Surfaces; 2007

Density Functional Theory study of the reaction pathways for HS <!-- @page { size: 8.5in 11in; margin: 0.79in } P { margin-bottom: 0.08in } --> Adsorption of S compounds on metal surfaces is of great interest due to several reasons: i) alkanethiols are the prototype components of supramolecular systems using self-assembled monolayers for surface functionalization and for the preparation of monolayer protected nanoparticles, ii) sulfur-containing molecules (e.g. SH2) are common impurities in fuels and oil-derived compounds used in the industry, that produce catalysts poisoning, etc. Density functional theory is used to investigate dissociative adsorption of H2S and HSCH3 on Au(111) at low coverages. The energetically most favorable reaction pathways for H-S bond cleavage are investigated using the Nudged Elastic Band (NEB) method. To evaluate substrate effects, for H2S we also consider adsorption on Cu(111). In the light of the comparison of results for H2S and HSCH3, the effect of the -CH3 group in the S-H bond cleavage process is analyzed.