甲硫醇在Cu(111)表面的解离吸附: 密度泛函理论研究

doi:10.3866/PKU.WHXB201211231

Abstract

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 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.

Key words: Methanethiol molecule, Cu(111) surface, Density functional theory, Adsorption geometry, Dissociation, Local density of states

MSC2000:

O641

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 Phys. -Chim. Sin., 2013, 29(02): 263-270.

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

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