B3LYP calculations of density functional theory （DFT）with 6-311+G（3df,2p）basis set level are used to investigate the equilibrium structures and intramolecular rearrangement reactions of the linear BrSSH and branched S=SBrH isomers.The calculated results shows that the linear structure is more stable than the branched structure (lower 73.1kJ·mol-1 corrected with zero point vibrational energy) energetically.The calculated energy barriers for the intramolecular bromine atom transfer and hydrogen atom transfer isomerization processes are 174.1kJ·mol-1 and 173.7kJ·mol-1,respectively.The kinetic results demonstrate that the isomerization is a unimolecular one,and the reaction rate is rather slow.It is consistent with thermodynomical results.So the isomerization process should proceed via the other likely processes.
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.
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.
The Cr doped into TiO2(110) surface has been studied systematically by using periodic DFT/B3LYP method with slab model. It is found that doping Cr into perfect TiO2 (110) surface can reduce the value of band-gap from 3.13 to 1.16 eV, and then photocatalysis reaction may be achieved in visual light area. The results are in good agreement with the experiments.
Adsorption behaviors of 2-bromothiophene on the Rh（111） surface were discussed with DFT. The results revealed that adsorption at the parallel hol site and bridge site was the most stable. After adsorption, bond length of 2-bromothiophene changed significantly. Molecular plane was distorted, and C-H （Br, S） in the molecule was oblique and upswept against the metal surface. Vertical adsorption site was less stable than the plane adsorption site, but there was no distortion for the thiophene ring after adsorption. Aromaticity of 2-bromothiophene was destroyed at the hol and bridge adsorption sites, and the carbon atom in the thiophene ring presented quasi-sp3 hybfidizaton. After adsorption at the parallel hol, 2-bromothiophene obtained 0.86 electrons in total, and Rh（111） surface lost 2.08 electrons in all.
