Citation: FAN Xiao-Li, LIU Yan, DU Xiu-Juan, LIU Chong, ZHANG Chao. Dissociative Adsorption of Methanethiol on Cu(111) Surface: a Density Functional Theory Study[J]. Acta Physico-Chimica Sinica, ;2013, 29(02): 263-270. doi: 10.3866/PKU.WHXB201211231 shu

Dissociative Adsorption of Methanethiol on Cu(111) Surface: a Density Functional Theory Study

1.
State Key Laboratory of Solidification Processing, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi’an 710072, P. R. China

Received Date: 13 August 2012
Available Online: 23 November 2012
Fund Project: 国家自然科学基金(20903075, 21273172) (20903075, 21273172)高等学校学科创新引智计划(111) (B08040) (111) (B08040)西北工业大学基础研究基金(JC20100226)资助项目 (JC20100226)

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 first 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 small shift toward the hollow site. The dissociative adsorption structure is thermodynamically 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.
- Methanethiol molecule,
- Cu(111) surface,
- Density functional theory,
- Adsorption geometry,
- Dissociation,
- Local density of states
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