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The stretching and breaking processes of stilbene-based molecular junctions, which contain S or N atoms in the terminal groups, are studied by using density functional theory. The numerical results show that for pyramid-shaped gold electrodes, a stretching force of about 0.59 nN is needed to break the molecular junction with —S terminals, which is larger than the force of 0.25 nN that is required by the molecule to stretch —SH terminals away from pyramid-shaped gold electrode. However, it is obviously smaller than the force of about 1.5 nN that is needed by the molecule to break —S terminals from planar-shaped gold electrode. If the terminal group is —NH2 or —NO2, the force for breaking the molecular junction is about 0.45 nN or 0.33 nN, respectively. More delocalized molecular orbitals formed by the coupling between the frontier occupied orbitals of molecule and electrodes, higher stretching force for breaking molecular junction is required. The natural bond orbital (NBO) analysis shows that more NBO net charges that the terminal atom possesses can enhance the stability of the molecule-electrode contact if there is no bonding orbital formed between end group of molecule and electrode. Based on the numerical results and the combination with previous studies, it can be found that —S terminal and —NH2 terminal show evident properties in distinguishing tip structures of gold electrodes, which provides useful information for precisely controlling the interactions and interface structures between molecule and electrodes.
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Keywords:
- single-molecule device /
- molecular junction stretching /
- molecular junction breaking /
- natural bond orbital /
- interface distinguishing
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表 1 M-S, M-SH, M-NH2和M-NO2体系分子与电极间的结合能、末端原子与电极间的成键轨道数、末端原子的孤对电子数以及末端原子的NBO净电荷数
Table 1. Binding energies between the molecules and the electrodes, the numbers of bonding orbitals between the terminal atoms and the electrodes, the numbers of lone electrons on the terminal atoms and the NBO net charges on the terminal atoms for M-S, M-SH, M-NH2 and M-NO2 molecular junctions.
体系 M-S M-SH M-NH2 M-NO2 结合能E/eV 0.505 0.229 0.277 0.186 成键轨道数 1 0 0 0 孤对电子数 2 2 1 3 NBO净电荷 S (–0.056) S (0.020) N (–0.910) O (–0.412) -
[1] Xu B, Tao N J 2003 Science 301 1221
Google Scholar
[2] Schneider N L, Johansson P, Berndt R 2013 Phys. Rev. B 87 045409
Google Scholar
[3] Rubio G, Agraït N, Vieira S 1996 Phys. Rev. Lett. 76 2302
Google Scholar
[4] Frei M, Aradhya S V, Koentopp M, Hybertsen M S, Venkataraman L 2011 Nano Lett. 11 1518
Google Scholar
[5] Reed M A, Zhou C, Muller C J, Burgin T P, Tour J M 1997 Science 278 252
Google Scholar
[6] Zhao Z K, Liu R, Mayer D, Coppola M, Sun L, Kim Y S, Wang C K, Ni L F, Chen X, Wang M N, Li Z L, Lee T, Xiang D 2018 Small 14 1703815
Google Scholar
[7] Liu R, Bi J J, Xie Z, Yin K K, Wang D Y, Zhang G P, Xiang D, Wang C K, Li Z L 2018 Phys. Rev. Applied 9 054023
Google Scholar
[8] Brandbyge M, Mozos J L, Ordejón P, Taylor J, Stokbro K 2002 Phys. Rev. B 65 165401
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[9] Li Z L, Zou B, Wang C K 2006 Phys. Rev. B 73 075326
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[10] Kang L S, Zhang Y H, Xu X L, Tang X 2017 Phys. Rev. B 96 235417
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[11] Miao Y Y, Qiu S, Zhang G P, Ren J F, Wang C K, Hu G C 2018 Phys. Rev. B 98 235415
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[12] 闫瑞, 吴泽文, 谢稳泽, 李丹, 王音 2018 物理学报 67 097301
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Yan R, Wu Z W, Xie W Z, Li D, Wang Y 2018 Acta Phys. Sin. 67 097301
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[13] Ji W F, Li Z L, Shen L, Kong D X, Zhang H Y 2007 J. Phys. Chem. B 111 485
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[25] Hu G C, Zhang Z, Li Y, Ren J F, Wang C K 2016 Chin. Phys. B 25 057308
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Google Scholar
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Google Scholar
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Google Scholar
[55] 樊帅伟, 王日高 2018 物理学报 67 213101
Google Scholar
Fan S W, Wang R G 2018 Acta Phys. Sin. 67 213101
Google Scholar
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Google Scholar
Liu R, Bao D L, Jiao Y, Wan L W, Li Z L, Wang C K 2014 Acta Phys. Sin. 63 068501
Google Scholar
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