甲硫醇在Au(111)表面不同覆盖度下吸附的第一性原理研究

doi:10.6023/A13010083

化学学报 ›› 2013, Vol. 71 ›› Issue (05): 829-836.DOI: 10.6023/A13010083 上一篇下一篇

研究论文

甲硫醇在Au(111)表面不同覆盖度下吸附的第一性原理研究

冉润欣, 范晓丽, 刘燕, 杨永良

西北工业大学材料学院凝固技术国家重点实验室西安 710072

投稿日期:2013-01-16 发布日期:2013-03-05
通讯作者: 范晓丽,xlfan@nwpu.edu.cn E-mail:xlfan@nwpu.edu.cn
基金资助:
项目受国家自然科学基金(Nos. 20903075, 21217372)和高等学校学科创新引智计划111 (No. B08040)资助.

Density Functional Theory Studies on the Adsorption of Methanethiol Molecule on Au(111) Surface at Different Coverage

Ran Runxin, Fan Xiaoli, Liu Yan, Yang Yongliang

State Key Laboratory of Solidification Processing, School of Material Science and Engineering, Northwestern Polytechnical University, Xi'an 710072

Received:2013-01-16 Published:2013-03-05
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 20903075, 21217372) and Program of Introducing Talents of Discipline to Universities, China (111 Project) (No. B08040).

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摘要/Abstract

采用第一性原理方法研究了五种覆盖度下甲硫醇在Au(111)面的吸附构型和吸附能. 分别对于S—H解离前CH₃SH和S—H解离后CH₃S, 计算其在不同覆盖度下的吸附结构和能量. 结果显示各种覆盖度下CH₃SH都优先吸附于top位, 倾斜角为70°±2°, 在低覆盖度(1/12, 1/9, 1/8)下的吸附能最大, 为0.33～0.35 eV; 而CH₃S在各种覆盖度下稳定吸附于bri-fcc位, 倾斜角为48.3°～58.5°, 低覆盖度下的吸附能为2.08 eV. 对于CH₃SH和CH₃S的吸附, 吸附能均随覆盖度的增大而减小. 重点研究了范德华力对高覆盖度吸附的影响. 在覆盖度为1/3时, 采用DFT-D2方法, 分别计算了CH₃SH和CH₃S的吸附, 结果显示范德华力使吸附物和Au表面的距离减小, 同时使CH₃SH和CH₃S的吸附能分别增大为0.59 eV和2.27 eV. DFT-D2方法修正使CH₃SH的结果更接近实验结论, 但使CH₃S的结果偏离实验值.

关键词: 密度泛函理论, 甲烷硫醇分子, Au(111)表面, 覆盖度, 范德华力, 吸附

By applying the first-principles method based on density functional theory, we have studied the adsorptions of non-dissociative CH₃SH molecule and dissociated CH₃S group on Au(111) surface at five different coverage (1/12, 1/8, 1/6, 1/4, 1/3). By performing the total energy calculations for both CH₃SH and CH₃S at four possible adsorption sites at every studied coverage, we have found the stable non-dissociative adsorption configuration, as well as the dissociated adsorption for CH₃SH from low to high coverage. Especially, the effect of van der Waals interaction on the adsorption configurations and energies have been studied by the DFT-D2 method. Our results suggest that the top site is most stable site for non-dissociative CH₃SH molecular at all the studied coverage, while the tilt angle of the adsorbed molecule is 70°±2°. The adsorption energy decreases with the increasing of the coverage, that is 0.33～0.35 eV at low coverage region of 1/12～1/8. On the other hand, the dissociated CH₃S group prefers to adsorb on bri-fcc site at all coverage with the tilt angle of 48.3°～58.5°. For the dissociated CH₃S, the adsorption energy also decreases with the increasing of the coverage, that is 2.07～2.08 eV at low coverage region of 1/12～1/8. At the saturated coverage of 1/3, the effect of van der Waals interaction was investigated for the adsorption of CH₃SH/Au(111) and CH₃S/Au(111) systems. The calculation results indicate that the van der Waals force makes the adsorbates closer to the substrate and the adsorption energy larger. The respective adsorption energies for CH₃SH and CH₃S are about 0.59 eV and 2.27 eV at coverage of 1/3. The calculation result by DFT-D2 method for CH₃SH agrees with the experimental conclusion, but that for CH₃S is away from the experimental observation. Moreover, our calculation results on the electronic structure show us that charge is transferred from the adsorbed CH₃SH and CH₃S to the Au substrate. And the amount of the transferred charge decrease with the increase of the coverage for both the CH₃SH and CH₃S, which imply that the interaction between the adsorbed CH₃SH/CH₃S and Au substrate decrease with the increasing of the coverage.

Key words: density functional theory, methanethiol molecule, Au(111) surface, coverage, van der Waals, adsorption

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冉润欣, 范晓丽, 刘燕, 杨永良. 甲硫醇在Au(111)表面不同覆盖度下吸附的第一性原理研究[J]. 化学学报, 2013, 71(05): 829-836.

Ran Runxin, Fan Xiaoli, Liu Yan, Yang Yongliang. Density Functional Theory Studies on the Adsorption of Methanethiol Molecule on Au(111) Surface at Different Coverage[J]. Acta Chimica Sinica, 2013, 71(05): 829-836.

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甲硫醇在Au(111)表面不同覆盖度下吸附的第一性原理研究

Density Functional Theory Studies on the Adsorption of Methanethiol Molecule on Au(111) Surface at Different Coverage

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