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 thiop...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.展开更多
Thiophene adsorption on the（111） surfaces of Pd and Pt have been investigated by density functional theory.The results indicate that the adsorption at the hollow sites is the most stable.To our interest,the molecula...Thiophene adsorption on the（111） surfaces of Pd and Pt have been investigated by density functional theory.The results indicate that the adsorption at the hollow sites is the most stable.To our interest,the molecular plane of thiophene ring is distorted with C=C bond being elongated to 1.450 and C–C bond being shortened to 1.347 ,and the C–H bonds tilt 13.91～44.05o away from this plane.Furthermore,analysis on population and density of states verified the calculated adsorption geometries.Finally,charge analysis suggests that thiophene molecule is an electron acceptor,reflecting the interaction between the lone pair of sulfur and the d-orbitals of metal.展开更多
基金supported by the Special Foundation for Young Scientists of Fuzhou University (XRC-0644)Sci & Tech Promotion Foundation of Fuzhou University (XJJ-0605)+3 种基金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)
文摘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.
基金Supported by the National Natural Science Foundation of China (No 20273013)the Important Special Foundation of Fujian Province (No 2005HZ01-2-6)the Natural Education Department Foundation of PhD Unit (No 20050386003)
文摘Thiophene adsorption on the（111） surfaces of Pd and Pt have been investigated by density functional theory.The results indicate that the adsorption at the hollow sites is the most stable.To our interest,the molecular plane of thiophene ring is distorted with C=C bond being elongated to 1.450 and C–C bond being shortened to 1.347 ,and the C–H bonds tilt 13.91～44.05o away from this plane.Furthermore,analysis on population and density of states verified the calculated adsorption geometries.Finally,charge analysis suggests that thiophene molecule is an electron acceptor,reflecting the interaction between the lone pair of sulfur and the d-orbitals of metal.
