物理化学学报Issue(2)：263-270,8.DOI:10.3866/PKU.WHXB201211231
甲硫醇在Cu（111）表面的解离吸附：密度泛函理论研究
Dissociative Adsorption of Methanethiol on Cu(111) Surface:a Density Functional Theory Study
摘要
Abstract
The interaction of methanethiol (CH3SH) molecules with the Cu(111) surface was investigated using a first-principles method based on density functional theory, and a slab model. A series of possible adsorption configurations constructed using S atoms on different sites with different tilt angles were studied. It was found for the fi rst time that the non-dissociative molecular adsorption of CH3SH on the Cu(111) surface with the S atom sitting on the top site belongs to the weak chemisorption, and the adsorption energy is 0.39 eV. After the dissociation of the S―H bond, the S atom is located at the bridge site, with a smal shift toward the hol ow site. The dissociative adsorption structure is thermodynamical y more stable than the intact one, and the adsorption energy is 0.75-0.77 eV. Two reaction pathways have been studied for the transition from non-dissociative adsorption to dissociative adsorption, and the activation energy barrier along the minimum energy path is 0.57 eV. The results of the calculations indicated that the released H atom prefers to form a bond with the copper surface, rather than desorbing in the H2 molecular form. Comparing the local density of states of S atoms in the single CH3SH, CH3SH/Cu(111), and CH3S/Cu(111) structures, we found that the bonding between the S atoms and the substrate is much stronger in the dissociated adsorption states.关键词
甲硫醇分子/Cu(111)表面/密度泛函理论/吸附构型/解离/局域态密度Key words
Methanethiol molecule/Cu(111) surface/Density functional theory/Adsorption geometry/Dissociation/Local density of states分类
化学化工引用本文复制引用
范晓丽,刘燕,杜秀娟,刘崇,张超..甲硫醇在Cu（111）表面的解离吸附：密度泛函理论研究[J].物理化学学报,2013,(2):263-270,8.基金项目
The project was supported by the National Natural Science Foundation of China (20903075,21273172), Program of Introducing Talents of Discipline to Universities, China (111 Project)(B08040), and Northwestern Polytechnical University Foundation for Fundamental Research, China (JC20100226).@@@@国家自然科学基金(20903075,21273172),高等学校学科创新引智计划(111)(B08040)及西北工业大学基础研究基金(JC20100226)资助项目 （20903075,21273172）
