Citation: FAN Xiao-Li, RAN Run-Xin, ZHANG Chao, YANG Yong-Liang. Density Functional Theory Study on the Adsorption of Dodecylthiol on Au(111) Surface[J]. Acta Physico-Chimica Sinica, ;2013, 29(09): 1907-1915. doi: 10.3866/PKU.WHXB201307022 shu

Density Functional Theory Study on the Adsorption of Dodecylthiol on Au(111) Surface

1.
State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an 710072, P. R. China

Received Date: 6 May 2013
Available Online: 2 July 2013
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)资助项目 (111)(B08040)

By applying the first-principles methods based on density functional theory and the slab model, we have studied the non-dissociative and dissociated adsorptions of a dodecylthiol (C₁₂H₂₅SH) molecule on Au(111) surface. Based on the calculated results, the fate of the H atom has been analyzed, and the longchain adsorption and short-chain adsorption have been compared. We have performed structure optimizations for a series of initial structures with the S atom located on different sites with different tilt angles. This structure optimizations gave two surface structures before and after the dissociation of S―H; the standing-up and lying-down adsorption structures. Our calculations indicate that the C₁₂H₂₅SH molecule prefers to stay on the top site, the corresponding adsorption energies are 0.35-0.38 eV. The dissociated C12H25S group prefers to adsorb on the bri-fcc site, with adsorption energies of 2.01-2.09 eV. We have compared the non-dissociative C₁₂H₂₅SH/Au(111) and dissociated C₁₂H₂₅S/Au(111) with the H atom adsorbing onto Au and desorbing as H₂, and found that the non-dissociative adsorption is more stable. The formation energy and the electronic structure showed that the non-dissociative adsorption belongs to the weak chemisorption, whereas the interaction between the S atom and Au surface becomes much stronger following cleavage of the S―H. A comparison of the adsorption of long-chain thiols on Au(111) surface with that of the short-chain thiols, indicates that the adsorption energies of the long-chain thiols are slightly larger, and the distances between the S atomand the surface Au atoms are slightly shorter.
- Density functional theory,
- Dodecylthiol,
- Au(111) surface,
- Adsorption structure,
- Lying-down configuration,
- Electronic structure
1. [1]
  
  (1) Ulman, A. Chem. Rev. 1996, 96, 1533. doi: 10.1021/cr9502357
2. [2]
  (2) Schreiber, F. Prog. Surf. Sci. 2000, 65, 151. doi: 10.1016/S0079-6816(00)00024-1
3. [3]
  (3) Schreiber, F. J. Phys.: Condes. Matter 2004, 16, R881.
4. [4]
  (4) Love, J. C.; Estroff, L. A.; Kriebel, J. K.; Nuzzo, R. G.;Whitesides, G. M. Chem. Rev. 2005, 105, 1103. doi: 10.1021/cr0300789
5. [5]
  (5) Nenchev, G.; Diaconescu, B.; Hagelberg, F.; Pohl, K. Phys. Rev. B 2009, 80, 081401. doi: 10.1103/PhysRevB.80.081401
6. [6]
  (6) Chen, W. K.; Cao, M. J.; Liu, S. H.; Xu, Y.; Li, Y.; Li, J. Q. Acta Phys. -Chim. Sin. 2005, 21, 903. [陈文凯, 曹梅娟, 刘书红,许莹,李奕,李俊篯. 物理化学学报, 2005, 21, 903.] doi: 10.3866/PKU.WHXB20050816
7. [7]
  (7) Cao, M. J.; Chen, W. K.; Liu, S. H.; Lu, C. H.; Xu, Y.; Li, J. Q.Chin. J. Catal. 2006, 27, 223. [曹梅娟, 陈文凯,刘书红, 陆春海,许莹,李俊篯.催化学报, 2006, 27, 223.]
8. [8]
  (8) Cao, M. J.; Chen, W. K.; Liu, S. H.; Xu, Y.; Li, J. Q. Acta Phys. -Chim. Sin. 2006, 22, 11. [曹梅娟, 陈文凯,刘书红,许莹,李俊篯. 物理化学学报, 2006, 22, 11.] doi: 10.3866/PKU.WHXB20060103
9. [9]
  (9) Li, B.; Zeng, C. G.; Li, Q. X.; Yang, J. L.; Hou, J. G.; Zhu, Q. S.J. Chin. Electr. Microsc. Soc. 2003, 22, 189. [李斌,曾长淦,李群祥, 杨金龙, 侯建国, 朱清时. 电子显微学报, 2003, 22,189.]
10. [10]
  (10) Yourdshahyan, Y.; Zhang, H. K.; Rappe, A. M. Phys. Rev. B2001, 63, 081405. doi: 10.1103/PhysRevB.63.081405
11. [11]
  (11) Vericat, C.; Vela, M. E.; Salvarezza, R. C. Phys. Chem. Chem. Phys. 2005, 7, 3258. doi: 10.1039/b505903h
12. [12]
  (12) Maksymovych, P.; Yates, J. T. J. Am. Chem. Soc. 2006, 128,10642. doi: 10.1021/ja062006f
13. [13]
  (13) Maksymovych, P.; Sorescu, D. C.; Yates, J. T. J. Phys. Chem. B2006, 110, 21161. doi: 10.1021/jp0625964
14. [14]
  (14) Maksymovych, P.; Vocnyy, O.; Dougherty, D. B.; Sorescu, D. C.;Yates, J. T. Pro. Surf. Sci. 2010, 85, 206. doi: 10.1016/j.progsurf.2010.05.001
15. [15]
  (15) Vericat, C.; Vela, M. E.; Benitez, G.; Carro, P.; Salvarezza, R. C.Chem. Soc. Rev. 2010, 39, 1805. doi: 10.1039/b907301a
16. [16]
  (16) Min, J. X.; Fan, X. L.; Cheng, Q. Z.; Chi, Q. Acta Chim. Sin.2011, 69, 789. [闵家祥, 范晓丽,程千忠,池琼.化学学报,2011, 69, 789.]
17. [17]
  (17) Carro, P.; Torres, D.; Diaz, R.; Salvarezza, R. C.; Lllas, F.J. Phys. Chem. Lett. 2012, 3, 2159. doi: 10.1021/jz300712g
18. [18]
  (18) Li, B.; Zeng, C. G.; Li, Q. X.; Wang, B.; Yuan, L. F.; Wang, H.Q.; Yang, J. L.; Hou, J. G.; Zhu, Q. S. J. Phys. Chem. B 2003,107, 972. doi: 10.1021/jp0261861
19. [19]
  (19) Wang, J. G.; Selloni, A. J. Phys. Chem. C 2007, 111, 12149. doi: 10.1021/jp0745891
20. [20]
  (20) Nakayz, M.; Shikishima, M.; Shibuta, M.; Hirata, N.; Eguchi,T.; Nakajima, A. ACS Nano 2012, 6, 8728. doi: 10.1021/nn302405r
21. [21]
  (21) Hohenberg, P.; Kohn, W. Phys. Rev. 1964, 136, B864.
22. [22]
  (22) Kohn, W.; Sham, L. J. Phys. Rev. 1965, 140, A1133.
23. [23]
  (23) Kresse, G.; Hafner, J. Phys. Rev. B 1993, 47, 558. doi: 10.1103/PhysRevB.47.558
24. [24]
  (24) Kresse, G.; Hafner, J. Phys. Rev. B 1994, 49, 14251. doi: 10.1103/PhysRevB.49.14251
25. [25]
  (25) Kresse, G.; Furthmüller, J. Phys. Rev. B 1996, 54, 11169.doi: 10.1103/PhysRevB.54.11169
26. [26]
  (26) Kresse, G.; Furthmüller, J. Comput. Mater. Sci. 1996, 6, 15.doi: 10.1016/0927-0256(96)00008-0
27. [27]
  (27) Kresse, G.; Joubert, D. Phys. Rev. B 1999, 59, 1758. doi: 10.1103/PhysRevB.59.1758
28. [28]
  (28) Blochl, P. E. Phys. Rev. B 1994, 50, 17953. doi: 10.1103/PhysRevB.50.17953
29. [29]
  (29) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996,77, 3865. doi: 10.1103/PhysRevLett.77.3865
30. [30]
  (30) Nara, J.; Higai, S.; Morikawa, Y.; Ohno, T. J. Chem. Phys. 2004,120, 6705. doi: 10.1063/1.1651064
31. [31]
  (31) Fan, X. L.; Chi, Q.; Liu, C.; Lau, W. J. Phys. Chem. C 2012,116, 1001.
32. [32]
  (32) Lustemberg, P. G.; Martiarena, M. L.; Martínez, A. E.;Busnen , H. F. Langmuir 2008, 24, 3274. doi: 10.1021/la703306t
33. [33]
  (33) Fan, X. L.; Zhang, C.; Liu, Y.; Lau, W. M. J. Phys. Chem. C2012, 116, 19909. doi: 10.1021/jp306812v
34. [34]
  (34) Maksymovych, P.; Yates, J. T. J. Am. Chem. Soc. 2008, 130,7518. doi: 10.1021/ja800577w
35. [35]
  (35) Rajaraman, G.; Caneschi, A.; Gatteschi, D.; Totti, F. Phys. Chem. Chem. Phys. 2011, 13, 3886. doi: 10.1039/c0cp02042g
36. [36]
  (36) Tielens, F.; Santos, E. J. Phys. Chem. C 2010, 114, 9444.
37. [37]
  (37) ttschalck, J.; Hammer, B. J. Chem. Phys. 2002, 116, 784.
38. [38]
  (38) Henkelman, G.; Arnaldsson, A.; Jonsson, H. Comput. Mater. Sci. 2006, 36, 354. doi: 10.1016/j.commatsci.2005.04.010
1. [1]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
2. [2]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
3. [3]
  Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166
4. [4]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
5. [5]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
6. [6]
  Xinyu Miao , Hao Yang , Jie He , Jing Wang , Zhiliang Jin . 调整Keggin型多金属氧酸盐电子结构构建S型异质结用于光催化析氢. Acta Physico-Chimica Sinica, 2025, 41(6): 100051-. doi: 10.1016/j.actphy.2025.100051
7. [7]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
8. [8]
  Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
9. [9]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
10. [10]
  Jiali CHEN , Guoxiang ZHAO , Yayu YAN , Wanting XIA , Qiaohong LI , Jian ZHANG . Machine learning exploring the adsorption of electronic gases on zeolite molecular sieves. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 155-164. doi: 10.11862/CJIC.20240408
11. [11]
  Jingwen Wang , Minghao Wu , Xing Zuo , Yaofeng Yuan , Yahao Wang , Xiaoshun Zhou , Jianfeng Yan . Advances in the Application of Electrochemical Regulation in Investigating the Electron Transport Properties of Single-Molecule Junctions. University Chemistry, 2025, 40(3): 291-301. doi: 10.12461/PKU.DXHX202406023
12. [12]
  Jiahong ZHENG , Jingyun YANG . Preparation and electrochemical properties of hollow dodecahedral CoNi₂S₄ supported by MnO₂ nanowires. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1881-1891. doi: 10.11862/CJIC.20240170
13. [13]
  Fei Xie , Chengcheng Yuan , Haiyan Tan , Alireza Z. Moshfegh , Bicheng Zhu , Jiaguo Yu . d带中心调控过渡金属单原子负载COF吸附O₂的理论计算研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2407013-. doi: 10.3866/PKU.WHXB202407013
14. [14]
  Qin Hu , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . Ni掺杂构建电子桥及激活MoS₂惰性基面增强光催化分解水产氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2406024-. doi: 10.3866/PKU.WHXB202406024
15. [15]
  Xinyu Yin , Haiyang Shi , Yu Wang , Xuefei Wang , Ping Wang , Huogen Yu . Spontaneously Improved Adsorption of H₂O and Its Intermediates on Electron-Deficient Mn^(3+δ)+ for Efficient Photocatalytic H₂O₂ Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312007-. doi: 10.3866/PKU.WHXB202312007
16. [16]
  Peng ZHOU , Xiao CAI , Qingxiang MA , Xu LIU . Effects of Cu doping on the structure and optical properties of Au₁₁(dppf)₄Cl₂ nanocluster. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1254-1260. doi: 10.11862/CJIC.20240047
17. [17]
  Xuyang Wang , Jiapei Zhang , Lirui Zhao , Xiaowen Xu , Guizheng Zou , Bin Zhang . Theoretical Study on the Structure and Stability of Copper-Ammonia Coordination Ions. University Chemistry, 2024, 39(3): 384-389. doi: 10.3866/PKU.DXHX202309065
18. [18]
  Hui Wang , Abdelkader Labidi , Menghan Ren , Feroz Shaik , Chuanyi Wang . 微观结构调控的g-C₃N₄在光催化NO转化中的最新进展：吸附/活化位点的关键作用. Acta Physico-Chimica Sinica, 2025, 41(5): 100039-. doi: 10.1016/j.actphy.2024.100039
19. [19]
  Yonghui ZHOU , Rujun HUANG , Dongchao YAO , Aiwei ZHANG , Yuhang SUN , Zhujun CHEN , Baisong ZHU , Youxuan ZHENG . Synthesis and photoelectric properties of fluorescence materials with electron donor-acceptor structures based on quinoxaline and pyridinopyrazine, carbazole, and diphenylamine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 701-712. doi: 10.11862/CJIC.20230373
20. [20]
  Liang MA , Honghua ZHANG , Weilu ZHENG , Aoqi YOU , Zhiyong OUYANG , Junjiang CAO . Construction of highly ordered ZIF-8/Au nanocomposite structure arrays and application of surface-enhanced Raman spectroscopy. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1743-1754. doi: 10.11862/CJIC.20240075

Get Citation

PDF

XML

Metrics

PDF Downloads(743)
Abstract views(1250)
HTML views(23)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142