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

doi:10.6023/A13010083

Acta Chimica Sinica ›› 2013, Vol. 71 ›› Issue (05): 829-836.DOI: 10.6023/A13010083 Previous Articles Next Articles

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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

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).

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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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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