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采用基于密度泛函理论的第一性原理方法研究了丙烷硫醇 (C3H7SH)在Au(111)面五种覆盖度(1/16, 2/16, 3/16, 4/16, 1/3) 下的未解离和解离吸附的结构、能量和吸附性质. 发现丙烷硫醇的倾斜角和吸附能均受覆盖度影响, 计算结果显示丙烷硫醇的倾斜角随着覆盖度的增大减小了6°–10°, 吸附能随覆盖度的增大减小了0.21 eV. 特别针对饱和覆盖度, 研究了三种可能的表面结构: (2√3×2√3 ight)R30°, 2√3×3和(3×3). 发现S–H键未解离时三种表面结构的吸附构型和吸附能基本一致; S–H键解离后, (2√3×2√3 ight)R30°和2√3×3结构的吸附能比以(3×3)结构的吸附能约高0.05–0.07 eV, 说明C3H7S在Au(111)面吸附时, 倾向于形成(2√3×2√3 ight)R30°和2√3×3结构. 此外, 采用DFT-D2方法对饱和覆盖度下C3H7SH分子在Au(111)面的吸附进行了范德华修正, 结果显示分子间相互作用使吸附物和Au表面的距离减小, 该相互作用对吸附能的修正值为0.53 eV, 修正后结果与实验结果接近.By applying the first-principles method based on the density functional theory, we study the non-dissociative adsorption of C3H7SH molecule and the dissociated adsorption of C3H7S group both on Au(111) surface at five kinds of coverages (1/16, 2/16, 3/16, 4/16, 1/3). It is found that both the tilt angle and the adsorption energy are affected by coverage. When the coverage increases to 1/3, the tilt angle of the molecular axis reduces 6°–10°, and the adsorption energy reduces 0.21 eV. At a saturated coverage, the absorption properties are especially studied for three Au(111) surface structures of (3×3), (2√3×2√3 ight)R30° and 2√3×3. For the non-dissociative adsorption of C3H7SH at the saturated coverage, both the adsorption configurations and adsorption energies are almost the same for the three surface structures. But for the dissociated C3H7S group, the adsorption energies of surface structures of (2√3×2√3 ight)R30° and 2√3×3 are about 0.05-0.07 eV higher than that of the (3×3) surface structure. Effects of the van der Waals interaction on the adsorption configuration and energy are investigated by the DFT-D2 method. For the non-dissociative adsorption of C3H7SH/Au(111) system at a saturated coverage of 1/3, the van der Waals interaction reduces the interaction distance between the adsorbate and the substrate, and corrects the adsorption energy by 0.53 eV, which is close to experimental result.
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Keywords:
- first principle /
- coverage /
- surface structure /
- van der Waals
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[1] Ulman A 1996 Chem. Rev. 96 1533
[2] Schreiber F 2000 Prog. Surf. Sci. 65 151
[3] Schreiber F 2004 J. Phys.: Condens. Matter 16 R881
[4] Love J C, Estroff L A, Kriebel J K, Nuzzo R G, Whitesides G M 2005 Chem. Rev. 105 1103
[5] Nenchev G, Diaconescu B, Hagelberg F, Pohl K 2009 Phys. Rev. B 80 081401
[6] Nuzzo R G, Allara D L 1983 J. Am. Chem. Soc. 105 4481
[7] Yang S R, Ren S L, Zhang J Y, Zhang X S 2001 Chem. J. Chin. Univ. 22 470 (in Chinese) [杨生荣, 任嗣利, 张俊彦, 张绪寿 2001 高等学校化学学报 22 470]
[8] Schreiber F, Eberhardt A, Leung T Y B, Schwartz P, Wetterer S M, Lavrich D J, Berman L, Fenter P, Eisenberger P, Scoles G 1998 Phys. Rev. B 57 12476
[9] Vericat C, Vela M E, Benitez G, Carro P, Salvarezza R C 2010 Chem. Soc. Rev. 39 1805
[10] Xu S, Cruchon S J N, Garno J C, Liu G Y, Jennings G K, Yong T H, Laibinis P E 1998 J. Chem. Phys. 108 5002
[11] Poirier G E, Pylant E D 1996 Science 272 1145
[12] Yamada R, Uosaki K 1998 Langmuir 14 855
[13] Wu T Q, Wang X Y, Jiao Z W, Luo H L, Zhu P 2013 Acta Phys. Sin. 62 186301 (in Chinese) [吴太权, 王新燕, 焦志伟, 罗宏雷, 朱萍 2013 62 186301]
[14] Li M, Zhang J Y, Zhang Y, Wang T M 2012 Chin. Phys. B 21 067302
[15] Niu W X, Zhang H 2012 Chin. Phys. B 21 026802
[16] Hu M, Wang W D, Zeng P, Zeng J, Qin Y X 2012 Chin. Phys. B 21 023101
[17] Yourdshahyan Y, Zhang H, Rappe A M 2001 Phys. Rev. B 63 081405
[18] Ran R X, Fan X L, Liu Y, Yang Y L 2013 Acta Chim. Sin. 71 829 (in Chinese) [冉润欣, 范晓丽, 刘燕, 杨永良 2013 化学学报 71 829]
[19] Luque N B, Santos E, Andres J, Tielens F 2011 Langmuir 27 14514
[20] Tielens F, Santos E 2010 J. Phys. Chem. C 114 9444
[21] Carla A A, Earl L S, Marc D P 1992 J. Am. Chem. Soc. 114 1222
[22] Touzov I, Gorman C B 1997 J. Phys. Chem. B 101 5263
[23] Li B, Bao S N, Cao P L, Zhuang Y Y 2003 Acta Phys. Sin. 52 202 (in Chinese) [李波, 鲍世宁, 曹培林, 庄友谊 2003 52 202]
[24] Yourdshahyan Y, Rappe A M 2002 J. Chem. Phys. 117 825
[25] Grimme S 2004 J. Comput. Chem. 25 1463
[26] Grimme S 2006 J. Comput. Chem. 27 1787
[27] Grimme S, Antony J, Ehrlich S, Krieg H 2010 J. Chem. Phys. 132 154104
[28] Dion M, Rydberg H, Schroder E, Langreth D C, Lundqvist B I 2004 Phys. Rev. Lett. 92 246401
[29] Hohenberg P, Kohn W 1964 Phys. Rev. B 136 B864
[30] Kohn W, Sham L J 1965 Phys. Rev. A 140 1133
[31] Kresse G, Furthmller J 1996 Phys. Rev. B 54 11169
[32] Kresse G, Furthmller J 1996 Comput. Mater. Sci. 6 15
[33] Kresse G, Hafner J 1993 Phys. Rev. B 47 558
[34] Kresse G, Hafner J 1994 Phys. Rev. B 49 14251
[35] Kresse G, Joubert D 1999 Phys. Rev. B 59 1758
[36] Blochl P E 1994 Phys. Rev. B 50 17953
[37] Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865
[38] Nara J, Higai S, Morikawa Y, Ohno T 2004 J. Chem. Phys. 120 6705
[39] Fan X L, Chi Q, Liu C, Lau W M 2012 J. Phys. Chem. C 116 1002
[40] Min J X, Fan X L, Cheng Q Z, Chi Q 2011 Acta Chim. Sin. 69 789 (in Chinese) [闵家祥, 范晓丽, 程千忠, 池琼 2011 化学学报 69 789]
[41] Lustemberg P G, Martiarena M L, Martínez A E, Busnengo H F 2008 Langmuir 24 3274
[42] Wang J G, Selloni A 2007 J. Phys. Chem. C 111 12149
[43] Carro P, Pensa E, Vericat C, Salvarezza R C 2013 J. Phys. Chem. C 117 2160
[44] Wu X X, Wang Q E, Wang F H, Zhou Y S 2010 Acta Phys. Sin. 59 7278 (in Chinese) [吴小霞, 王乾恩, 王福合, 周云生 2010 59 7278]
[45] Zeng Z H, Deng H Q, Li W X, Hu W Y 2006 Acta Phys. Sin. 55 3157 (in Chinese) [曾振华, 邓辉球, 李微雪, 胡望宇 2006 55 3157]
[46] Xu G G, Wu Q Y, Zhang J M, Chen Z G, Huang Z G 2009 Acta Phys. Sin. 58 1924 (in Chinese) [许桂贵, 吴青云, 张建敏, 陈志高, 黄志高 2009 58 1924]
[47] Lavrich D J, Wetterer S M, Bernasek S L, Scoles G 1998 J. Phys. Chem. B 102 3456
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