密度泛函理论研究十二烷硫醇在Au(111)面上的吸附

doi:10.3866/PKU.WHXB201307022

物理化学学报 >> 2013, Vol. 29 >> Issue (09): 1907-1915.doi: 10.3866/PKU.WHXB201307022

密度泛函理论研究十二烷硫醇在Au(111)面上的吸附

范晓丽, 冉润欣, 张超, 杨永良

西北工业大学, 凝固技术国家重点实验室, 西安 710072

收稿日期:2013-05-06 修回日期:2013-07-01 发布日期:2013-08-28
通讯作者: 范晓丽 E-mail:xlfan@nwpu.edu.cn
基金资助:
国家自然科学基金(20903075, 21273172)及高等学校学科创新引智计划(111)(B08040)资助项目

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

FAN Xiao-Li, RAN Run-Xin, ZHANG Chao, YANG Yong-Liang

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

Received:2013-05-06 Revised:2013-07-01 Published:2013-08-28
Contact: FAN Xiao-Li E-mail:xlfan@nwpu.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China (20903075, 21273172) and Program of Introducing Talents of Discipline to Universities, China (111 Project) (B08040).

摘要/Abstract

摘要：

采用第一性原理方法研究了十二烷硫醇(C₁₂H₂₅SH)分子在Au(111)面上未解离和解离吸附的结构、能量和吸附性质,在此基础上分析判断长链硫醇分子在Au(111)面吸附时S―H键的解离, 以及分子链长度对吸附结构和能量的影响. 计算了S原子在不同位置以不同方式吸附的系列构型, 结果表明在S―H键解离前和解离后,均存在两种可能的表面结构, 直立吸附构型和平铺吸附构型; 未解离的C₁₂H₂₅SH分子倾向于吸附在top位, 吸附能为0.35-0.38 eV; H原子解离后C₁₂H₂₅S基团倾向于吸附在bri-fcc位, 吸附能量为2.01-2.09 eV. 比较分析未解离吸附和解离吸附, 发现C₁₂H₂₅SH分子未解离吸附相较于解离吸附要稳定, 未解离吸附属于弱化学吸附.局域电子态密度和差分电荷密度分析进一步验证了S―H解离后S原子与表面之间成键的数目增加, 而且键合更强. 同时我们发现长链硫醇的吸附能量较短链硫醇的吸附能量略大, S原子与表面Au原子之间的距离略小.

关键词: 密度泛函理论, 十二烷硫醇, Au(111)面, 吸附结构, 平铺构型, 电子结

Abstract:

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.

Key words: Density functional theory, Dodecylthiol, Au(111) surface, Adsorption structure, Lying-down configuration, Electronic structure

MSC2000:

O641

范晓丽, 冉润欣, 张超, 杨永良. 密度泛函理论研究十二烷硫醇在Au(111)面上的吸附[J]. 物理化学学报, 2013, 29(09): 1907-1915.

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 Phys. -Chim. Sin., 2013, 29(09): 1907-1915.

参考文献

(1) Ulman, A. Chem. Rev. 1996, 96, 1533. doi: 10.1021/cr9502357
(2) Schreiber, F. Prog. Surf. Sci. 2000, 65, 151. doi: 10.1016/S0079-6816(00)00024-1
(3) Schreiber, F. J. Phys.: Condes. Matter 2004, 16, R881.
(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) Nenchev, G.; Diaconescu, B.; Hagelberg, F.; Pohl, K. Phys. Rev. B 2009, 80, 081401. doi: 10.1103/PhysRevB.80.081401
(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) 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) 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) 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) Yourdshahyan, Y.; Zhang, H. K.; Rappe, A. M. Phys. Rev. B2001, 63, 081405. doi: 10.1103/PhysRevB.63.081405
(11) Vericat, C.; Vela, M. E.; Salvarezza, R. C. Phys. Chem. Chem. Phys. 2005, 7, 3258. doi: 10.1039/b505903h
(12) Maksymovych, P.; Yates, J. T. J. Am. Chem. Soc. 2006, 128,10642. doi: 10.1021/ja062006f
(13) Maksymovych, P.; Sorescu, D. C.; Yates, J. T. J. Phys. Chem. B2006, 110, 21161. doi: 10.1021/jp0625964
(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) Vericat, C.; Vela, M. E.; Benitez, G.; Carro, P.; Salvarezza, R. C.Chem. Soc. Rev. 2010, 39, 1805. doi: 10.1039/b907301a
(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) Carro, P.; Torres, D.; Diaz, R.; Salvarezza, R. C.; Lllas, F.J. Phys. Chem. Lett. 2012, 3, 2159. doi: 10.1021/jz300712g
(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) Wang, J. G.; Selloni, A. J. Phys. Chem. C 2007, 111, 12149. doi: 10.1021/jp0745891
(20) Nakayz, M.; Shikishima, M.; Shibuta, M.; Hirata, N.; Eguchi,T.; Nakajima, A. ACS Nano 2012, 6, 8728. doi: 10.1021/nn302405r
(21) Hohenberg, P.; Kohn, W. Phys. Rev. 1964, 136, B864.
(22) Kohn, W.; Sham, L. J. Phys. Rev. 1965, 140, A1133.
(23) Kresse, G.; Hafner, J. Phys. Rev. B 1993, 47, 558. doi: 10.1103/PhysRevB.47.558
(24) Kresse, G.; Hafner, J. Phys. Rev. B 1994, 49, 14251. doi: 10.1103/PhysRevB.49.14251
(25) Kresse, G.; Furthmüller, J. Phys. Rev. B 1996, 54, 11169.doi: 10.1103/PhysRevB.54.11169
(26) Kresse, G.; Furthmüller, J. Comput. Mater. Sci. 1996, 6, 15.doi: 10.1016/0927-0256(96)00008-0
(27) Kresse, G.; Joubert, D. Phys. Rev. B 1999, 59, 1758. doi: 10.1103/PhysRevB.59.1758
(28) Blochl, P. E. Phys. Rev. B 1994, 50, 17953. doi: 10.1103/PhysRevB.50.17953
(29) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996,77, 3865. doi: 10.1103/PhysRevLett.77.3865
(30) Nara, J.; Higai, S.; Morikawa, Y.; Ohno, T. J. Chem. Phys. 2004,120, 6705. doi: 10.1063/1.1651064
(31) Fan, X. L.; Chi, Q.; Liu, C.; Lau, W. J. Phys. Chem. C 2012,116, 1001.
(32) Lustemberg, P. G.; Martiarena, M. L.; Martínez, A. E.;Busnengo, H. F. Langmuir 2008, 24, 3274. doi: 10.1021/la703306t
(33) Fan, X. L.; Zhang, C.; Liu, Y.; Lau, W. M. J. Phys. Chem. C2012, 116, 19909. doi: 10.1021/jp306812v
(34) Maksymovych, P.; Yates, J. T. J. Am. Chem. Soc. 2008, 130,7518. doi: 10.1021/ja800577w
(35) Rajaraman, G.; Caneschi, A.; Gatteschi, D.; Totti, F. Phys. Chem. Chem. Phys. 2011, 13, 3886. doi: 10.1039/c0cp02042g
(36) Tielens, F.; Santos, E. J. Phys. Chem. C 2010, 114, 9444.
(37) Gottschalck, J.; Hammer, B. J. Chem. Phys. 2002, 116, 784.
(38) Henkelman, G.; Arnaldsson, A.; Jonsson, H. Comput. Mater. Sci. 2006, 36, 354. doi: 10.1016/j.commatsci.2005.04.010

[1]	李亚文, 那广仁, 罗树林, 贺欣, 张立军. 全无机卤化铅钙钛矿的结构、热力学稳定性和电子性质[J]. 物理化学学报, 2021, 37(4): 2007015 -0 .
[2]	王云飞, 刘建华, 于美, 钟锦岩, 周琪森, 邱俊明, 张晓亮. SnO₂表面卤化提高钙钛矿太阳能电池光伏性能[J]. 物理化学学报, 2021, 37(3): 2006030 -0 .
[3]	李诗涵,赵侦超,李世坤,邢友东,张维萍. DFT计算结合固体NMR研究富铝SSZ-13的铝分布和Brønsted酸性[J]. 物理化学学报, 2020, 36(4): 1903021 -0 .
[4]	王亦清,沈少华. 非金属掺杂石墨相氮化碳光催化的研究进展与展望[J]. 物理化学学报, 2020, 36(3): 1905080 -0 .
[5]	肖雪珠, 曹小芳, 赵东波, 荣春英, 刘述斌. 运用概念密度泛函理论和信息论方法定量描述胺类分子的分子碱度[J]. 物理化学学报, 2020, 36(11): 1906034 -0 .
[6]	黄智超,戴亚中,温晓杰,刘丹,林宇轩,徐珍,裴坚,吴凯. Au(111)表面Verdazyl自由基的构象转换[J]. 物理化学学报, 2020, 36(1): 1907043 -0 .
[7]	陈强,姜利学,李海方,陈娇娇,赵艳霞,何圣贵. 钒硼双原子阳离子活化甲烷研究[J]. 物理化学学报, 2019, 35(9): 1014 -1020 .
[8]	王丹,丁迅雷,廖珩璐,戴佳钰. 单个金或银原子掺杂的氧化钒团簇上的甲烷活化反应[J]. 物理化学学报, 2019, 35(9): 1005 -1013 .
[9]	韩萌茹,周亚男,周旋,储伟. 通过g-C₃N₄担载MNi₁₂ (Fe, Co, Cu, Zn)纳米团簇调节甲烷化[J]. 物理化学学报, 2019, 35(8): 850 -857 .
[10]	赵越,崔佳桐,胡继闯,马嘉璧. VO_1-4⁺阳离子与n-C_mH_2m+2 (m = 3, 5, 7)烷烃的反应性研究：氧含量和碳链长度的影响[J]. 物理化学学报, 2019, 35(5): 531 -538 .
[11]	毕富珍,郑晓,任志勇. 甲胺基-甲脒基混合钙钛矿的第一性原理研究[J]. 物理化学学报, 2019, 35(1): 69 -75 .
[12]	奚晋扬,中村悠马,赵天琦,王冬,帅志刚. 石墨炔与锡烯层状体系的形变势和电声耦合及载流子传输理论研究[J]. 物理化学学报, 2018, 34(9): 961 -976 .
[13]	许文武,高嶷. 巯基保护的中空金纳米球[J]. 物理化学学报, 2018, 34(7): 770 -775 .
[14]	卢天,陈沁雪. 通过价层电子密度分析展现分子电子结构[J]. 物理化学学报, 2018, 34(5): 503 -513 .
[15]	尹玥琪,蒋梦绪,刘春光. Keggin型多酸负载的单原子催化剂(M₁/POM, M = Ni, Pd, Pt, Cu, Ag, Au, POM = [PW₁₂O₄₀]^3-)活化氮气分子的密度泛函理论计算研究[J]. 物理化学学报, 2018, 34(3): 270 -277 .

密度泛函理论研究十二烷硫醇在Au(111)面上的吸附

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

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

本文评价

推荐阅读 0