Molecular structure and electronic spectrum of MoS<sub>2</sub>under external electric field

Du Jian-Bin; Feng Zhi-Fang; Zhang Qian; Han Li-Jun; Tang Yan-Lin; Li Qi-Feng

doi:10.7498/aps.68.20190781

Abstract

A variety of new materials have improved the production and life of human beings. Two-dimensional nano materials have become a research hotspot due to their unique physical and chemical properties. Molybdenum disulfide (MoS₂) is representative of transition metal sulfide, with excellent mechanical properties and chemical stability. In order to study the influence of external electrical field on the molecular structure and spectrum, here in this work, the density functional theory with the hybrid B3LYP at Def2-TZVP level is employed to calculate the geometrical parameters of the ground state of MoS₂ molecule under external electric fields ranging from 0 to 0.1 a.u. (0−5.1423 × 10¹⁰ V/m). Based on the optimized structures, the time-dependent density functional theory at the same level as the above is adopted to calculate the absorption wavelengths and the molar absorption coefficients for the first ten excited states of MoS₂ molecule under external electric fields. The results show that the most strongest absorption band is located at 483 nm with a molar absorption coefficient of 461 L·mol^–1·cm^–1 in the UV-Vis absorption spectrum. The intramolecular charge transfers as a whole with the enhancement of the external electric field. The electric dipole moment increases with the external electric field rising, while the total molecular energy decreases with external electric field increasing. With the enhancement of the external electric field, the absorption peaks show a significant redshift. When the electric field increases to 0.1 a.u., the redshift is obvious. This can be explained as follows. When the external electric field is weaker, the electron transfer in the molecule is not significant. However, with the augment of the external electric field, the electron transfer in the molecule occurs as a whole. This makes the electron interaction between Mo and S weaker, thus the electron transition is more likely to occur. The energy required for excitation is reduced, and the wavelength of the excited state becomes longer, that is, the absorption peak takes a redshift. With the enhancement of the external electric field, the molar absorption coefficient increases obviously. This is because the overall transfer of the external electric field to the electron makes the electron cloud density of the MoS₂ molecule increase and the number of electrons in transition augment. This work provides a theoretical basis for the utilization and improvement of MoS₂ photoelectric properties, and also enlightens the application research of other photoelectric materials.

Keywords:

Authors and contacts

1.
School of Precision Instrument and Optoelectronics Engineering, Tianjin University, Tianjin 300072, China
2.
College of Science, Langfang Normal University, Langfang 065000, China
3.
College of Physics, Guizhou University, Guiyang 550025, China

Corresponding author: Li Qi-Feng, qfli@tju.edu.cn

Funds: Project supported by the National Key Research and Development Program of China (Grant Nos. 2014YQ060773, 2017YFC0803600).

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References

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Cited By

图 1 MoS₂的分子结构

Figure 1. Structure of the MoS₂ molecule.

DownLoad: Full-Size Img PowerPoint

图 2 MoS₂分子占据轨道侧视图

Figure 2. The side view of MoS₂ occupied molecular orbital.

DownLoad: Full-Size Img PowerPoint

图 3 分子电偶极矩u随外电场的变化

Figure 3. The relation of dipole moment and electric field intensity of MoS₂.

DownLoad: Full-Size Img PowerPoint

图 4 外电场下分子总能量E的变化

Figure 4. The relationship between total energy of MoS₂ molecule and electric field intensity.

DownLoad: Full-Size Img PowerPoint

图 5 不同外电场下的MoS₂分子UV-Vis吸收光谱(Epsilon: 摩尔吸收系数)

Figure 5. UV-Vis absorption spectra of MoS₂ molecule under different external electric fields (Epsilon: molar absorption coefficient).

DownLoad: Full-Size Img PowerPoint

图 6 不同外电场下MoS₂激发态的分子轨道(占据轨道, 填充了电子的分子轨道; 跃迁轨道, 分子被激发时, 电子从占据轨道跃迁到的空轨道; 轨道权重, 分子某一激发态, 构成轨道的各个组成部分的贡献, 图中给出的是所占比例最大的部分)

Figure 6. Excited state orbital diagram of MoS₂ molecule under different external electric fields (occupied orbitals, molecular orbitals filled with electrons; a transition orbital is a vacant orbital that an electron jumps from an occupied orbital to when a molecule is excited; orbital weight, the contribution of each component of an excited state of a molecule to the composition of the orbital, shown in the figure is the one with the largest proportion).

DownLoad: Full-Size Img PowerPoint

表 1 不同电场下原子Mo和S的电荷Q/a.u.

Table 1. The charges of Mo and S (unit: a.u.) of the MoS₂ molecule under different external electric fields.

F 0 0.02 0.04 0.06 0.08 0.10

1Mo 0.782 0.752 0.659 0.488 0.237 –0.069
2S –0.391 –0.376 –0.329 –0.244 –0.119 0.034
3S –0.391 –0.376 –0.329 –0.244 –0.119 0.034

DownLoad: CSV

[1]	Ayari A, Cobas E, Ogundadegbe O, Fuhrer M S 2007 J. Appl. Phys. 101 014507 Google Scholar
[2]	Radisavljevic B, Radenovic A, Brivio J, Giacometti V, Kis A 2011 Nat. Nanotechnol. 6 147 Google Scholar
[3]	陈敏强 2017 硕士学位论文 (太原: 太原理工大学) Chen M Q 2017 M. S. Thesis (Taiyuan: Taiyuan University of Technology) (in Chinese)
[4]	Dominko R, Arcon D, Mrzel A, Zorko A, Cevc P, Venturini P, Gaberscek M, Remskar M, Mihailovic D 2002 Adv. Mater. 14 1531 Google Scholar
[5]	孙华婷 2018 硕士学位论文 (合肥: 安徽大学) Sun H T 2018 M. S. Thesis (Hefei: Anhui University) (in Chinese)
[6]	Mohammad H, Amir B F, Narayana R A 2015 Nat. Comms. 6 8616 Google Scholar
[7]	Li W F, Yang Y M, Weber J K, Zhang G, Zhou R H 2016 ACS Nano 10 1829 Google Scholar
[8]	Jafar A, Alireza K 2017 Comput. Mater. Sci. 137 201 Google Scholar
[9]	Mateus H K, Jose R B, Marcia C B 2018 J. Chem. Phys. 148 222804 Google Scholar
[10]	Wang P, Li W, Du C C, Zheng X, Sun X L, Yan Y G, Zhang J 2017 Comput. Mater. Sci. 140 284 Google Scholar
[11]	Zhang Y D, Meng Z S, Shi Q, Gao H Q, Liu Y Z, Wang Y H, Rao D W, Deng K M, Lu R F 2017 J. Phys.: Condens. Matter 29 375201 Google Scholar
[12]	Ellert C, Corkum P B 1999 Phys. Rev. A 59 R3170 Google Scholar
[13]	王藩侯, 黄多辉, 杨俊升 2013 物理学报 62 073102 Google Scholar Wang F H, Huang D H, Yang J S 2013 Acta Phys. Sin. 62 073102 Google Scholar
[14]	Ledingham K W D, Singhal R P, Smith D J, McCanny T, Graham P, Kilic H S, Peng W X, Wang S L, Langley A J, Taday P F, Kosmidis C 1998 J. Phys. Chem. A 102 3002 Google Scholar
[15]	Rai D, Joshi H, Kulkarni A D, Gejji S P, Pathak R K 2007 J. Phys. Chem. A 111 9111 Google Scholar
[16]	Iwamae A, Hishikawa A, Yamanouchi K 2000 J. Phys. B: At. Mol. Opt. Phys. 33 223 Google Scholar
[17]	Ellert C, Stapelfeldt H, Constant E 1998 Phil. Trans. R. Sol. Lond. A 356 329 Google Scholar
[18]	杜建宾, 冯志芳, 韩丽君, 唐延林, 武德起 2018 物理学报 67 223101 Google Scholar Du J B, Feng Z F, Han L J, Tang Y L, Wu D Q 2018 Acta Phys. Sin. 67 223101 Google Scholar
[19]	李世雄, 吴永刚, 令狐荣锋, 孙光宇, 张正平, 秦水介 2015 物理学报 64 043101 Google Scholar Li S X, Wu Y G, Linghu R F, Sun G Y Zhang Z P, Qin S J 2015 Acta Phys. Sin. 64 043101 Google Scholar
[20]	谢安东, 谢晶, 周玲玲, 伍冬兰, 阮文, 罗文浪 2016 原子与分子物理学报 33 989 Xie A D, Xie J, Zhou L L, Wu D L, Ruan W, Luo W L 2016 Chin. J. Atom. Mol. Phys. 33 989
[21]	Liu Q H, Li L Z, Li Y F, Gao Z X, Chen Z F, Lu J 2012 J. Phys. Chem. C 116 21556 Google Scholar
[22]	Gemming S, Seifert G, Götz M, Fischer T, Ganteför G 2010 Phys. Status Solidi B 247 1069 Google Scholar
[23]	Peverati R, Truhlar D G 2012 Phys. Chem. Chem. Phys. 14 13171 Google Scholar
[24]	Liang B Y, Andrews L 2002 J. Phys. Chem. A 106 6945 Google Scholar
[25]	Mayhall N J, Becher E L, Chowdhury A, Raghavachari K 2011 J. Phys. Chem. A 115 2291 Google Scholar
[26]	Wang B, Wu N, Zhang X B, Huang X, Zhang Y F, Chen W K, Ding K N 2013 J. Phys. Chem. A 117 5632 Google Scholar
[27]	Wang Y Y, Deng J J, Wang X, Che J T, Ding X L 2018 Phys. Chem. Chem. Phys. 20 6365 Google Scholar
[28]	Wu D L, Tan B, Wan H J, Zang X Q, Xie A D 2013 Chin. Phys. B 22 123101 Google Scholar
[29]	Grozema F C, Telesca R, Joukman H T, Snijders J G 2001 J. Chem. Phys. 115 10014 Google Scholar
[30]	朱正和, 付依备, 高涛, 陈银亮, 陈晓军 2003 原子与分子物理学报 20 169 Google Scholar Zhu Z H, Fu Y B, Gao T, Chen Y L, Chen X J 2003 Chin. J. Atom. Mol. Phys. 20 169 Google Scholar
[31]	Gemming S, Tamuliene J, Seifert G, Bertram N, Kim Y D, Ganteför G, 2006 Appl. Phys. A: Mater. Sci. Process. 82 161 Google Scholar
[32]	Murugan P, Kumar V, Kawazoe Y, Ota N 2005 Phys. Rev. A: At. Mol. Opt. Phys. 71 063203 Google Scholar
[33]	Jelena P, Jasna V, Tijana T I, Marko S, Radoš G 2018 Opt. Quant. Electron. 50 291 Google Scholar

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Molecular structure and electronic spectrum of MoS₂under external electric field

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Corresponding author: Li Qi-Feng, qfli@tju.edu.cn

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F	0	0.02	0.04	0.06	0.08	0.10
1Mo	0.782	0.752	0.659	0.488	0.237	–0.069
2S	–0.391	–0.376	–0.329	–0.244	–0.119	0.034
3S	–0.391	–0.376	–0.329	–0.244	–0.119	0.034

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Molecular structure and electronic spectrum of MoS2under external electric field

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Corresponding author: Li Qi-Feng, qfli@tju.edu.cn

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Molecular structure and electronic spectrum of MoS₂under external electric field