Ab initio modeling of xanthate adsorption on ZnS surfaces

Detta är en avhandling från Luleå : Luleå tekniska universitet

Sammanfattning: Modeling surface adsorption requires systems of hundreds of atoms. To model such systems at an ab initio level successfully, we need to avoid traditional quantum chemical methods. In the present work we have shown that density functional theory is a powerful modeling tool for large chemical systems especially in combinations with pseudopotentials This is validated by an initial study of ethyl and heptyl xanthates and their sodium/potassium salts. In this study, all electron calculations using both Hartree-Fock and density functional theory methods are compared with experimental infrared results. To do this the influence of basis sets and modeling approaches on the geometrical structure and the vibrational modes are examined. This includes comparing the pseudopotential and full electron potential approaches. Results obtained from pseudopotential methods are in close agreement with both all electron calculations as well as experimental results, here used to study adsorption of heptyl xanthate ZnS surfaces. Vibrational frequencies of the adsorbed species is presented, together with calculations of the tilt angles. The investigation of the tilt angles resulted in 20.3° 20.6° and 25.2° for the 100, 110 and 111 surfaces respectively. Heptyl xanthate forms a bridging confirmation on both the 110 and 111 surfaces and a bidentate confirmation on the 100 surface. Assignments of vibrational modes of ethyl/heptyl xanthate molecule and its corresponding potassium/sodium salts are also reported.