基于曲率和电子结构的掺杂C<sub>50</sub>和C<sub>70</sub>富勒烯的稳定性研究

引用本文: 包金小, 王晓霞, 吴铜伟, 贾桂霄, 章永凡. 基于曲率和电子结构的掺杂C₅₀和C₇₀富勒烯的稳定性研究[J]. 物理化学学报, 2015, 31(5): 899-904. doi: 10.3866/PKU.WHXB201503201 shu

Citation: BAO Jin-Xiao, WANG Xiao-Xia, WU Tong-Wei, JIA Gui-Xiao, ZHANG Yong-Fan. Stability of Doped C₅₀ and C₇₀ Based on Curvature and Electronic Structures[J]. Acta Physico-Chimica Sinica, 2015, 31(5): 899-904. doi: 10.3866/PKU.WHXB201503201 shu

基于曲率和电子结构的掺杂C₅₀和C₇₀富勒烯的稳定性研究

基金项目:
内蒙古科技大学材料与冶金学院青年人才孵化器基金(2014CY012) (2014CY012)

内蒙古自治区高等学校科学技术研究项目基金(NJZZ13128) (NJZZ13128)

内蒙古自治区自然科学基金(2014BS0507)资助项目 (2014BS0507)

摘要:

使用密度泛函理论(DFT)-B3LYP/6-31G^*方法研究了B、N、Si、P和Co在C₅₀和C₇₀中的掺杂能和电子结构, 并基于曲率理论和电子结构探讨了掺杂富勒烯的结构稳定性. 计算结果表明, 掺杂能随着原子曲率的增大而减小, 随着掺杂物种原子半径的增大而增大, B、N、P和Co的掺杂有利于C₅₀结构的稳定, 而B和N的掺杂不利于C₇₀结构的稳定; 除了用于反映原子活性的曲率主要决定掺杂反应性, 各不等价碳原子在C₅₀和C₇₀的最高占据分子轨道(HOMO)中所占成分对掺杂能的影响也很大, 且其成分越大越有利于掺杂. 此外, 掺杂原子得失电子情况与其电负性有关. 本工作将为富勒烯结构稳定性的研究提供理论依据.

关键词:

富勒烯
/ 掺杂
/ 曲率理论
/ 稳定性
/ 电子结构

English

Stability of Doped C₅₀ and C₇₀ Based on Curvature and Electronic Structures

1.
1 School of Materials and Metallurgy, Inner Mon lia University of Science and Technology, Baotou 014010, Inner Mong l Autonomous Region, P. R. China;
2 Department of Chemistry, Fuzhou University, Fuzhou 350108, P. R. China
Received Date: 24 November 2014
Available Online: 08 May 2015
Fund Project:
内蒙古科技大学材料与冶金学院青年人才孵化器基金(2014CY012)

内蒙古自治区高等学校科学技术研究项目基金(NJZZ13128)

内蒙古自治区自然科学基金(2014BS0507)资助项目

Abstract:

The doping energies and electronic structures of B, N, Si, P, and Co in C₅₀ and C₇₀ were investigated using the density functional theory (DFT)-B3LYP/6-31G^* method, and the structural stabilities of doped fullerenes were investigated based on curvature theory and the electronic structures. The calculated results showed that the doping energies decreased with increasing curvature, and increased with increasing atomic radius of the doping species. Doping with B, N, P, and Co stabilized the C₅₀ structure. However, doping with B and N was disadvantageous for the structural stability of C₇₀. The doping reactivities were mainly determined by the curvature and related to the percentage of nonequivalent carbon atoms in the highest occupied molecular orbital (HOMO), and a large percentage was beneficial for the doping stability. In addition, whether the doped atoms accepted or lost electrons depended on their electronegativity. This work will be helpful for the stabilization of fullerene structures in experiment.

Key words:

1. [1]
  
  (1) Kroto, H.W. Nature 1987, 329, 529. doi: 10.1038/329529a0
  (1) Kroto, H.W. Nature 1987, 329, 529. doi: 10.1038/329529a0
2. [2]
  (2) Albertazzi, E.; Domene, C.; Fowler, P.W.; Heine, T.; Seifert, G.; Van Alsenoy, C.; Zerbetto, F. Phys. Chem. Chem. Phys. 1999, 12, 2913.(2) Albertazzi, E.; Domene, C.; Fowler, P.W.; Heine, T.; Seifert, G.; Van Alsenoy, C.; Zerbetto, F. Phys. Chem. Chem. Phys. 1999, 12, 2913.
3. [3]
  (3) Lu, X.; Chen, Z. F. Chem. Rev. 2005, 105, 3643. doi: 10.1021/cr030093d(3) Lu, X.; Chen, Z. F. Chem. Rev. 2005, 105, 3643. doi: 10.1021/cr030093d
4. [4]
  (4) Li, J. Q.; Jia, G. X.; Zhang, Y. F. Chem. Eur. J. 2007, 13, 6430.(4) Li, J. Q.; Jia, G. X.; Zhang, Y. F. Chem. Eur. J. 2007, 13, 6430.
5. [5]
  (5) Xie, S. Y.; Gao, F.; Lu, X.; Bin, R. B.; Wang, C. R.; Zhang, X.; Liu, M. L.; Deng, S. L.; Zheng, L. S. Science 2004, 304, 699. doi: 10.1126/science.1095567(5) Xie, S. Y.; Gao, F.; Lu, X.; Bin, R. B.; Wang, C. R.; Zhang, X.; Liu, M. L.; Deng, S. L.; Zheng, L. S. Science 2004, 304, 699. doi: 10.1126/science.1095567
6. [6]
  (6) Hummelen, J. C.; Bellavia-Lund, C.; Wudl, F. Top. Curr. Chem. 1999, 199, 93. doi: 10.1007/3-540-68117-5(6) Hummelen, J. C.; Bellavia-Lund, C.; Wudl, F. Top. Curr. Chem. 1999, 199, 93. doi: 10.1007/3-540-68117-5
7. [7]
  (7) Hirsch, A.; Brettreich, M. Heterofullerenes. Fullerenes, Chemistry and Reactions, 2nd ed.; Wiley-VCH:Weinheim, Germany, 2005; p 359.(7) Hirsch, A.; Brettreich, M. Heterofullerenes. Fullerenes, Chemistry and Reactions, 2nd ed.; Wiley-VCH:Weinheim, Germany, 2005; p 359.
8. [8]
  (8) Hirsch, A.; Nuber, B. Accounts Chem. Res. 1999, 32, 795. doi: 10.1021/ar980113b(8) Hirsch, A.; Nuber, B. Accounts Chem. Res. 1999, 32, 795. doi: 10.1021/ar980113b
9. [9]
  (9) Vostrowsky, O.; Hirsch, A. Chem. Rev. 2006, 106, 5191. doi: 10.1021/cr050561e(9) Vostrowsky, O.; Hirsch, A. Chem. Rev. 2006, 106, 5191. doi: 10.1021/cr050561e
10. [10]
  (10) Clemmer, D. E.; Hunter, J. M.; Shelimov, K. B.; Jarrold, M. F. Nature 1994, 372, 248. doi: 10.1038/372248a0(10) Clemmer, D. E.; Hunter, J. M.; Shelimov, K. B.; Jarrold, M. F. Nature 1994, 372, 248. doi: 10.1038/372248a0
11. [11]
  (11) Kong, Q.; Shen, Y.; Zhao, L.; Zhuang, J.; Qian, S.; Li, Y.; Lin, Y.; Cai, R. J. Chem. Phys. 2002, 116, 128.(11) Kong, Q.; Shen, Y.; Zhao, L.; Zhuang, J.; Qian, S.; Li, Y.; Lin, Y.; Cai, R. J. Chem. Phys. 2002, 116, 128.
12. [12]
  (12) Ding, C. G.; Yang, J. L.; Han, R. S.; Wang, K. L. Phys. Rev. A 2001, 64, 043201.(12) Ding, C. G.; Yang, J. L.; Han, R. S.; Wang, K. L. Phys. Rev. A 2001, 64, 043201.
13. [13]
  (13) Viani, L.; Dos Santos, M. C. Solid State Commun. 2006, 138, 498. doi: 10.1016/j.ssc.2006.04.027(13) Viani, L.; Dos Santos, M. C. Solid State Commun. 2006, 138, 498. doi: 10.1016/j.ssc.2006.04.027
14. [14]
  (14) Yang, Z. Y.; Xu, X. F.; Wang, G. C.; Shang, Z. F.; Cai, Z. S.; Pan, Y. M.; Zhao, X. Z. J. Mol. Struct.: Theochem 2002, 618, 191. doi: 10.1016/S0166-1280(02)00402-5(14) Yang, Z. Y.; Xu, X. F.; Wang, G. C.; Shang, Z. F.; Cai, Z. S.; Pan, Y. M.; Zhao, X. Z. J. Mol. Struct.: Theochem 2002, 618, 191. doi: 10.1016/S0166-1280(02)00402-5
15. [15]
  (15) Kurita, N.; Koboyyashi, K.; Kumabora, H.; Ta , K.; Ozawa, K. Chem. Phys. Lett. 1992, 198, 95. doi: 10.1016/0009-2614(92)90054-Q(15) Kurita, N.; Koboyyashi, K.; Kumabora, H.; Ta , K.; Ozawa, K. Chem. Phys. Lett. 1992, 198, 95. doi: 10.1016/0009-2614(92)90054-Q
16. [16]
  (16) Wang, S. H.; Chen, F.; Fann, Y. C.; Kashani, M.; Malaty, M.; Jansen, S. A. J. Phys. Chem. 1995, 99, 6801. doi: 10.1021/j100018a008(16) Wang, S. H.; Chen, F.; Fann, Y. C.; Kashani, M.; Malaty, M.; Jansen, S. A. J. Phys. Chem. 1995, 99, 6801. doi: 10.1021/j100018a008
17. [17]
  (17) Ewels, C. P. Nano Lett. 2006, 6, 890. doi: 10.1021/nl051421n(17) Ewels, C. P. Nano Lett. 2006, 6, 890. doi: 10.1021/nl051421n
18. [18]
  (18) Zuo, T. M.; Xu, L. S.; Beavers, C. M.; Olmstead, M. M.; Fu, W. J.; Crawford, D.; Balch, A. L.; Dorn, H. C. J. Am. Chem. Soc. 2008, 130, 12992. doi: 10.1021/ja802417d(18) Zuo, T. M.; Xu, L. S.; Beavers, C. M.; Olmstead, M. M.; Fu, W. J.; Crawford, D.; Balch, A. L.; Dorn, H. C. J. Am. Chem. Soc. 2008, 130, 12992. doi: 10.1021/ja802417d
19. [19]
  (19) Stevenson, S.; Ling, Y.; Coumbe, C. E.; Mackey, M. A.; Confait, B. S.; Phillips, J. P.; Dorn, H. C.; Zhang, Y. J. Am. Chem. Soc. 2009, 131, 17780. doi: 10.1021/ja908370t(19) Stevenson, S.; Ling, Y.; Coumbe, C. E.; Mackey, M. A.; Confait, B. S.; Phillips, J. P.; Dorn, H. C.; Zhang, Y. J. Am. Chem. Soc. 2009, 131, 17780. doi: 10.1021/ja908370t
20. [20]
  (20) Breslavskaya, N. N.; Levin, A. A.; Buchachenko, A. L. Russ. Chem. Bull. 2004, 53, 18. doi: 10.1023/B:RUCB.0000024824.35542.0e(20) Breslavskaya, N. N.; Levin, A. A.; Buchachenko, A. L. Russ. Chem. Bull. 2004, 53, 18. doi: 10.1023/B:RUCB.0000024824.35542.0e
21. [21]
  (21) Chen, Z.; Jiao, H.; Buhl, M.; Hirsch, A.; Thiel, W. Theor. Chem. Acc. 2001, 106, 352. doi: 10.1007/s002140100284(21) Chen, Z.; Jiao, H.; Buhl, M.; Hirsch, A.; Thiel, W. Theor. Chem. Acc. 2001, 106, 352. doi: 10.1007/s002140100284
22. [22]
  (22) Hauke, F.; Hirsch, A.; Liu, S. G.; Eche yen, L.; Swartz, A.; Luo, C.; Guldi, D. M. Chem. Phys. Chem. 2002, 3, 195.(22) Hauke, F.; Hirsch, A.; Liu, S. G.; Eche yen, L.; Swartz, A.; Luo, C.; Guldi, D. M. Chem. Phys. Chem. 2002, 3, 195.
23. [23]
  (23) Vougioukalakis, G. C.; Orfanopoulos, M. J. Am. Chem. Soc. 2004, 126, 15956. doi: 10.1021/ja045495x(23) Vougioukalakis, G. C.; Orfanopoulos, M. J. Am. Chem. Soc. 2004, 126, 15956. doi: 10.1021/ja045495x
24. [24]
  (24) Vougioukalakis, G. C.; Hatzimarinaki, M.; Lykakis, I. N.; Orfanopoulos, M. J. Org. Chem. 2006, 71, 829. doi: 10.1021/jo051838d(24) Vougioukalakis, G. C.; Hatzimarinaki, M.; Lykakis, I. N.; Orfanopoulos, M. J. Org. Chem. 2006, 71, 829. doi: 10.1021/jo051838d
25. [25]
  (25) Chen, C. B. Synthesis, Isolation and Properties of Titanium- Based Novel Endohedral Fullerenes. Ph. D. Dissertation, University of Science and Technology of China, Hefei, 2011. [陈传宝. 含金属钛的新型内嵌富勒烯的合成, 分离及性质研 [D]. 合肥: 中国科技大学, 2011.](25) Chen, C. B. Synthesis, Isolation and Properties of Titanium- Based Novel Endohedral Fullerenes. Ph. D. Dissertation, University of Science and Technology of China, Hefei, 2011. [陈传宝. 含金属钛的新型内嵌富勒烯的合成, 分离及性质研 [D]. 合肥: 中国科技大学, 2011.]
26. [26]
  (26) Jia, G. X.; Li, X. G.; Song, X.W.; Li, J. Q.; Chen, Y. Surf. Sci. 2013, 608, 122. doi: 10.1016/j.susc.2012.09.025(26) Jia, G. X.; Li, X. G.; Song, X.W.; Li, J. Q.; Chen, Y. Surf. Sci. 2013, 608, 122. doi: 10.1016/j.susc.2012.09.025
27. [27]
  (27) Branz, W.; Billas, I. M. L.; Malinowski, N.; Tast, F.; Heinebrodt, M.; Martin, T. P. J. Chem. Phys. 1998, 109, 3425. doi: 10.1063/1.477410(27) Branz, W.; Billas, I. M. L.; Malinowski, N.; Tast, F.; Heinebrodt, M.; Martin, T. P. J. Chem. Phys. 1998, 109, 3425. doi: 10.1063/1.477410
28. [28]
  (28) Jia, G. X. Electronic Structures of Carbon Nanotubes and Fullerenes and Chemical Anisotropies: A Density Functional Theory Study. Ph. D. Dissertation, Fuzhou University, Fuzhou, 2007. [贾桂霄. 碳纳米管和富勒烯的电子结构及其化学各向异性的理论研究[D]. 福州: 福州大学, 2007.](28) Jia, G. X. Electronic Structures of Carbon Nanotubes and Fullerenes and Chemical Anisotropies: A Density Functional Theory Study. Ph. D. Dissertation, Fuzhou University, Fuzhou, 2007. [贾桂霄. 碳纳米管和富勒烯的电子结构及其化学各向异性的理论研究[D]. 福州: 福州大学, 2007.]
29. [29]
  (29) Axel, D. B. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913(29) Axel, D. B. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
30. [30]
  (30) Lu, X.; Chen, Z. F.; Thiel, W.; Schleyer, P. v. R.; Huang, R. B.; Zheng, L. S. J. Am. Chem. Soc. 2004, 126, 14871. doi: 10.1021/ja046725a(30) Lu, X.; Chen, Z. F.; Thiel, W.; Schleyer, P. v. R.; Huang, R. B.; Zheng, L. S. J. Am. Chem. Soc. 2004, 126, 14871. doi: 10.1021/ja046725a
31. [31]
  (31) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03, Revision B.05; Gaussian Inc.: Pittsburgh, PA, 2003.
  (31) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03, Revision B.05; Gaussian Inc.: Pittsburgh, PA, 2003.

扫一扫看文章

计量

PDF下载量: 232
文章访问数: 787
HTML全文浏览量: 57

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

基于曲率和电子结构的掺杂C₅₀和C₇₀富勒烯的稳定性研究

English

Stability of Doped C₅₀ and C₇₀ Based on Curvature and Electronic Structures

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

基于曲率和电子结构的掺杂C50和C70富勒烯的稳定性研究

English

Stability of Doped C50 and C70 Based on Curvature and Electronic Structures

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

基于曲率和电子结构的掺杂C₅₀和C₇₀富勒烯的稳定性研究

Stability of Doped C₅₀ and C₇₀ Based on Curvature and Electronic Structures

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs