A DFT Study of Thiophene Adsorption on the Rh(111) Surfaces  

作　　者：陈展虹 丁开宁 徐香兰 李俊篯 

机构地区：[1]Department of Chemistry,Fuzhou University [2]Department of Information Technology,Fujian Education College

出　　处：《Chinese Journal of Structural Chemistry》2010年第1期93-101,共9页结构化学（英文）

基　　金：supported by the Special Foundation for Young Scientists of Fuzhou University (XRC-0644);Sci & Tech Promotion Foundation of Fuzhou University (XJJ-0605);the Key Project of Fujian Province (2005HZ01-2-6);Ph D Programs Foundation of Ministry of Education of China (20050386003);the National Natural Science Foundation of China (20273013);Natural Science Foundation of Fujian Province (2002F010)

摘　　要：Thiophene adsorption on the Rh（111） surfaces has been investigated by density functional theory.The results show that the adsorption at the hollow and bridge sites is the most stable.The molecular plane of the thiophene ring is distorted,the C=C bond is stretched to 1.448 and the C–C bond is shortened to 1.390.The C–H bonds tilt 22～42oaway from the surface.The calculated adsorption geometries are in reasonable agreement with population analysis and density of states.The thiophene molecule obtains 0.74 electrons, reflecting the interaction between the lone pair of sulfur and the d-orbitals of metal. The reaction paths and transition states for desulfurization of the molecule have been investigated. The bridge adsorption structure of thiophene leads to a thiol via an activated reaction with an energetic barrier of 0.30 eV. This second step is slightly difficult, and dissociation into a C4H4 fragment and a sulfur atom is possible, with an energetic barrier of 0.40 eV.Thiophene adsorption on the Rh（111） surfaces has been investigated by density functional theory.The results show that the adsorption at the hollow and bridge sites is the most stable.The molecular plane of the thiophene ring is distorted,the C=C bond is stretched to 1.448 and the C–C bond is shortened to 1.390.The C–H bonds tilt 22～42oaway from the surface.The calculated adsorption geometries are in reasonable agreement with population analysis and density of states.The thiophene molecule obtains 0.74 electrons, reflecting the interaction between the lone pair of sulfur and the d-orbitals of metal. The reaction paths and transition states for desulfurization of the molecule have been investigated. The bridge adsorption structure of thiophene leads to a thiol via an activated reaction with an energetic barrier of 0.30 eV. This second step is slightly difficult, and dissociation into a C4H4 fragment and a sulfur atom is possible, with an energetic barrier of 0.40 eV.

关 键 词：THIOPHENE RHODIUM DFT CALCULATIONS ADSORPTION （111） surface 

分 类 号：O647.31[理学—物理化学]