甲硫醇在Cu(111)表面的解离吸附: 密度泛函理论研究

引用本文: 范晓丽, 刘燕, 杜秀娟, 刘崇, 张超. 甲硫醇在Cu(111)表面的解离吸附: 密度泛函理论研究[J]. 物理化学学报, 2013, 29(02): 263-270. doi: 10.3866/PKU.WHXB201211231 shu

Citation: 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 Physico-Chimica Sinica, 2013, 29(02): 263-270. doi: 10.3866/PKU.WHXB201211231 shu

甲硫醇在Cu(111)表面的解离吸附: 密度泛函理论研究

基金项目:
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) (111) (B08040)

西北工业大学基础研究基金(JC20100226)资助项目 (JC20100226)

摘要:

采用基于密度泛函理论的第一性原理方法和平板模型研究了CH₃SH分子在Cu(111)表面的吸附反应.系统地计算了S原子在不同位置以不同方式吸附的一系列构型, 第一次得到未解离的CH₃SH分子在Cu(111)表面顶位上的稳定吸附构型,该构型吸附属于弱的化学吸附, 吸附能为0.39 eV. 计算同时发现在热力学上解离结构比未解离结构更加稳定. 解离的CH₃S吸附在桥位和中空位之间, 吸附能为0.75-0.77 eV. 计算分析了未解离吸附到解离吸附的两条反应路径, 最小能量路径的能垒为0.57 eV. 计算结果还表明S―H键断裂后的H原子并不是以H₂分子的形式从表面解吸附而是以与表面成键的形式存在. 通过比较S原子在独立的CH₃SH分子和吸附状态下的局域态密度, 发现S―H键断裂后S原子和表面的键合强于未断裂时S原子和表面的键合.

关键词:

English

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

1.
State Key Laboratory of Solidification Processing, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi’an 710072, P. R. China
Received Date: 13 August 2012
Available Online: 14 January 2013
Fund Project:
国家自然科学基金(20903075, 21273172)

高等学校学科创新引智计划(111) (B08040)

西北工业大学基础研究基金(JC20100226)资助项目

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:

1. [1]
  
  (1) Ulman, A. Chem. Rev. 1996, 96, 1533. doi: 10.1021/cr9502357
  (1) Ulman, A. Chem. Rev. 1996, 96, 1533. doi: 10.1021/cr9502357
2. [2]
  (2) Rzeznicka, I.; Lee, J.; Maksymovych, P.; Yates, J. T. J. Phys. Chem. B 2005, 109, 15992. doi: 10.1021/jp058124r(2) Rzeznicka, I.; Lee, J.; Maksymovych, P.; Yates, J. T. J. Phys. Chem. B 2005, 109, 15992. doi: 10.1021/jp058124r
3. [3]
  (3) Fan, X. L.; Liu, Y.; Liu, C.; Liu, H. M. Acta Phys. -Chim. Sin.2012, 28, 1107. [范晓丽, 刘燕, 刘崇, 刘焕明. 物理化学学报, 2012, 28, 1107.] doi: 10.3866/PKU.WHXB201203011(3) Fan, X. L.; Liu, Y.; Liu, C.; Liu, H. M. Acta Phys. -Chim. Sin.2012, 28, 1107. [范晓丽, 刘燕, 刘崇, 刘焕明. 物理化学学报, 2012, 28, 1107.] doi: 10.3866/PKU.WHXB201203011
4. [4]
  (4) Floriano, P. N.; Schlieben, O.; Doomes, E. E.; Klein, I.; Janssen,J.; Hormes, J.; Poliakoff, E. D.; McCarley, R. L. Chem. Phys. Lett. 2000, 321, 175. doi: 10.1016/S0009-2614(00)00311-0(4) Floriano, P. N.; Schlieben, O.; Doomes, E. E.; Klein, I.; Janssen,J.; Hormes, J.; Poliakoff, E. D.; McCarley, R. L. Chem. Phys. Lett. 2000, 321, 175. doi: 10.1016/S0009-2614(00)00311-0
5. [5]
  (5) Toomes, R. L.; Polcik, M.; Kittel, M.; Hoeft, J. T.; Saya , D. I.;Pascal, M.; Lamont, J. Robinson, C. L. A.;Woodruff, D. P. Surf. Sci. 2002, 513, 437. doi: 10.1016/S0039-6028(02)01736-3(5) Toomes, R. L.; Polcik, M.; Kittel, M.; Hoeft, J. T.; Saya , D. I.;Pascal, M.; Lamont, J. Robinson, C. L. A.;Woodruff, D. P. Surf. Sci. 2002, 513, 437. doi: 10.1016/S0039-6028(02)01736-3
6. [6]
  (6) Zhou, J. G; Hagelberg, F. Phys. Rev. Lett. 2006, 97, 045505. doi: 10.1103/PhysRevLett.97.045505(6) Zhou, J. G; Hagelberg, F. Phys. Rev. Lett. 2006, 97, 045505. doi: 10.1103/PhysRevLett.97.045505
7. [7]
  (7) Nara, J.; Higai, S.; Morikawa, Y.; Ohno, T. Chem. Phys. 2004,120, 6705.(7) Nara, J.; Higai, S.; Morikawa, Y.; Ohno, T. Chem. Phys. 2004,120, 6705.
8. [8]
  (8) Lee, J. G.; Yates, J. T. J. Phys. Chem. B 2003, 107, 10540. doi: 10.1021/jp0302515(8) Lee, J. G.; Yates, J. T. J. Phys. Chem. B 2003, 107, 10540. doi: 10.1021/jp0302515
9. [9]
  (9) Lai, Y. H.; Yeh, C. T.; Cheng, S. H.; Liao, P.; Hung,W. H.J. Phys. Chem. B 2002, 106, 5438. doi: 10.1021/jp0146869(9) Lai, Y. H.; Yeh, C. T.; Cheng, S. H.; Liao, P.; Hung,W. H.J. Phys. Chem. B 2002, 106, 5438. doi: 10.1021/jp0146869
10. [10]
  (10) Driver, S. M.; King, D. A. Surf. Sci. 2007, 601, 510. doi: 10.1016/j.susc.2006.10.013(10) Driver, S. M.; King, D. A. Surf. Sci. 2007, 601, 510. doi: 10.1016/j.susc.2006.10.013
11. [11]
  (11) Imanishi, A.; Isawa, K.; Matsui, F.; Tsuduki, T.; Yokoyama, T.;Kondoh, H.; Kitajima, Y.; Ohta, T. Surf. Sci. 1998, 407, 282.doi: 10.1016/S0039-6028(98)00217-9(11) Imanishi, A.; Isawa, K.; Matsui, F.; Tsuduki, T.; Yokoyama, T.;Kondoh, H.; Kitajima, Y.; Ohta, T. Surf. Sci. 1998, 407, 282.doi: 10.1016/S0039-6028(98)00217-9
12. [12]
  (12) Jackson, G. J.;Woodruff, D. P.; Jones, R. G.; Singh, N. K.;Chan, A. S. Y.; Cowie, B. C. C.; Formoso, V. Phys. Rev. Lett.2000, 84, 119. doi: 10.1103/PhysRevLett.84.119(12) Jackson, G. J.;Woodruff, D. P.; Jones, R. G.; Singh, N. K.;Chan, A. S. Y.; Cowie, B. C. C.; Formoso, V. Phys. Rev. Lett.2000, 84, 119. doi: 10.1103/PhysRevLett.84.119
13. [13]
  (13) D'A stino, S.; Chiodo, L.; Sala, F. D.; Cin lani, R.; Rinaldi,R. Phys. Rev. B 2007, 75, 195444. doi: 10.1103/PhysRevB.75.195444(13) D'A stino, S.; Chiodo, L.; Sala, F. D.; Cin lani, R.; Rinaldi,R. Phys. Rev. B 2007, 75, 195444. doi: 10.1103/PhysRevB.75.195444
14. [14]
  (14) Kariapper, M. S.; Grom, G. F.; Jackson, G. J.; McConville, C.F.;Woodruff, D. P. J. Phys. Condes. Matter 1998, 10, 8661. doi: 10.1088/0953-8984/10/39/005(14) Kariapper, M. S.; Grom, G. F.; Jackson, G. J.; McConville, C.F.;Woodruff, D. P. J. Phys. Condes. Matter 1998, 10, 8661. doi: 10.1088/0953-8984/10/39/005
15. [15]
  (15) Zhou, J. G.;Williams, Q. L.; Hagelberg, F. Phys. Rev. B 2008,77, 035402. doi: 10.1103/PhysRevB.77.035402(15) Zhou, J. G.;Williams, Q. L.; Hagelberg, F. Phys. Rev. B 2008,77, 035402. doi: 10.1103/PhysRevB.77.035402
16. [16]
  (16) Syed, J. A.; Sardar, S. A.; Yagi, S.; Tanaka, K. Thin Solid Films2006, 515, 2130. doi: 10.1016/j.tsf.2006.08.004(16) Syed, J. A.; Sardar, S. A.; Yagi, S.; Tanaka, K. Thin Solid Films2006, 515, 2130. doi: 10.1016/j.tsf.2006.08.004
17. [17]
  (17) Kresse, G.; Furthmüller, J. Phys. Rev. B 1996, 54, 11169. doi: 10.1103/PhysRevB.54.11169(17) Kresse, G.; Furthmüller, J. Phys. Rev. B 1996, 54, 11169. doi: 10.1103/PhysRevB.54.11169
18. [18]
  (18) Hohenberg, P.; Kohn,W. Phys. Rev. B 1964, 136, B864.(18) Hohenberg, P.; Kohn,W. Phys. Rev. B 1964, 136, B864.
19. [19]
  (19) Kresse, G.; Joubert, D. Phys. Rev. B 1999, 59, 1758. doi: 10.1103/PhysRevB.59.1758(19) Kresse, G.; Joubert, D. Phys. Rev. B 1999, 59, 1758. doi: 10.1103/PhysRevB.59.1758
20. [20]
  (20) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996,77, 3865. doi: 10.1103/PhysRevLett.77.3865(20) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996,77, 3865. doi: 10.1103/PhysRevLett.77.3865
21. [21]
  (21) Monkhorst, H.; Pack, J. Phys. Rev. B 1976, 13, 5188. doi: 10.1103/PhysRevB.13.5188(21) Monkhorst, H.; Pack, J. Phys. Rev. B 1976, 13, 5188. doi: 10.1103/PhysRevB.13.5188
22. [22]
  (22) Jónsson, H. Annu . Rev. Phys. Chem. 2000, 51, 623. doi: 10.1146/annurev.physchem.51.1.623(22) Jónsson, H. Annu . Rev. Phys. Chem. 2000, 51, 623. doi: 10.1146/annurev.physchem.51.1.623
23. [23]
  (23) Henkelman, G.; Uberuaga, B. P.; Jónsson, H. Chem. Phys. 2000,113, 9901.(23) Henkelman, G.; Uberuaga, B. P.; Jónsson, H. Chem. Phys. 2000,113, 9901.
24. [24]
  (24) Vanderbilt, D. Phys. Rev. B 1990, 41, 7892. doi: 10.1103/PhysRevB.41.7892(24) Vanderbilt, D. Phys. Rev. B 1990, 41, 7892. doi: 10.1103/PhysRevB.41.7892
25. [25]
  (25) Huang, Y. L.; Liu, Z. P. Acta Phys. -Chim. Sin. 2008, 24, 1662.[黄永丽, 刘志平. 物理化学学报, 2008, 24, 1662.] doi: 10.3866/PKU.WHXB20080923(25) Huang, Y. L.; Liu, Z. P. Acta Phys. -Chim. Sin. 2008, 24, 1662.[黄永丽, 刘志平. 物理化学学报, 2008, 24, 1662.] doi: 10.3866/PKU.WHXB20080923
26. [26]
  (26) Favot, F.; Corso, A. D.; Baldereschi, A. Chem. Phys. 2001, 114,483.(26) Favot, F.; Corso, A. D.; Baldereschi, A. Chem. Phys. 2001, 114,483.
27. [27]
  (27) 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.](27) 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.]
28. [28]
  (28) Cometto, F. P.; Olivera, P. P.; Macagno, V. A.; Patrito, E. M.J. Phys. Chem. B 2005, 109, 21737. doi: 10.1021/jp053273v(28) Cometto, F. P.; Olivera, P. P.; Macagno, V. A.; Patrito, E. M.J. Phys. Chem. B 2005, 109, 21737. doi: 10.1021/jp053273v
29. [29]
  (29) Xia,W. S.;Wang, H. Y.;Wang, H. L.; Zhang, Q. E. Chem. J. Chin. Univ. 1998, 19, 438. [夏文生, 汪海有, 万惠霖, 张乾二.高等学校化学学报, 1998, 19, 438.](29) Xia,W. S.;Wang, H. Y.;Wang, H. L.; Zhang, Q. E. Chem. J. Chin. Univ. 1998, 19, 438. [夏文生, 汪海有, 万惠霖, 张乾二.高等学校化学学报, 1998, 19, 438.]
30. [30]
  (30) Lustemberg, P. G.; Martiarena, M. L.; Martinez, A. E.;Busnen , H. F. Langmuir 2008, 24, 3274. doi: 10.1021/la703306t
  (30) Lustemberg, P. G.; Martiarena, M. L.; Martinez, A. E.;Busnen , H. F. Langmuir 2008, 24, 3274. doi: 10.1021/la703306t

扫一扫看文章

计量

PDF下载量: 1321
文章访问数: 2538
HTML全文浏览量: 129

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

甲硫醇在Cu(111)表面的解离吸附: 密度泛函理论研究

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

甲硫醇在Cu(111)表面的解离吸附: 密度泛函理论研究

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs