金属硫化物富勒烯Sc2S@C90的结构与性质

doi:10.6023/A14060448

化学学报 ›› 2014, Vol. 72 ›› Issue (10): 1105-1109.DOI: 10.6023/A14060448 上一篇下一篇

研究论文

金属硫化物富勒烯Sc₂S@C₉₀的结构与性质

雷丹, 赵冲, 甘利华

西南大学化学化工学院重庆 400715

投稿日期:2014-06-09 修回日期:2014-08-25 发布日期:2014-08-25
通讯作者: 甘利华 E-mail:ganlh@swu.edu.cn
基金资助:
项目受国家自然科学基金(No. 51272216)和中央高校基金(No. XDJK2014B032)资助.

Structures and Properties of Metal Sulfide Fullerene Sc₂S@C₉₀

Lei Dan, Zhao Chong, Gan Lihua

School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715

Received:2014-06-09 Revised:2014-08-25 Published:2014-08-25
Supported by:
Project supported by the National Natural Science Foundation of China (No. 51272216) and the Fundamental Research Funds for the Central Universities of China (No. XDJK2014B032).

文章分享

1. 金属硫化物富勒烯Sc₂S@C₉₀的结构与性质.PDF(120KB)

摘要/Abstract

Sc₂S@C₉₀存在的信号已经被质谱检测到，但其结构还没有得到表征. 为了研究Sc₂S@C₉₀的结构和性质，通过密度泛函理论计算方法对Sc₂S@C₉₀的异构体进行了系统的筛选. 计算结果表明，能量最低的两个异构体分别为Sc₂S@C₉₀：99913和Sc₂S@C₉₀：99915. 对Sc₂S@C₉₀在0到4000 K温度下的相对浓度进行了评估，结果显示，Sc₂S@C₉₀：99913和Sc₂S@C₉₀：99915可以在高温下共存. 分析研究了Sc₂S@C₉₀的内嵌团簇与碳笼间的键连关系和相互作用特性. 这些研究可为Sc₂S@C₉₀的结构确定提供指导.

关键词: 内嵌富勒烯, Sc₂S@C₉₀, 密度泛函理论, 相对浓度, QTAIM

Metallic sulfide fullerene Sc₂S@C₉₀ has been detected by mass spectra but not been isolated and structurally characterized. It is impossible to perform extensive tests on Sc₂S@C₉₀ due to its low yield, quantum chemical calculations thus become an important method to predict or identify its structure and properties. Here a systematic density functional theory study are first performed on 15756 isomers of fullerene C90 and their anions with 0～3 pairs of fused-pentagons, then 30 isomers of metallic sulfide fullerenes Sc₂S@C₉₀ are constructed by putting Sc2S into the selected candidate cages with different orientations and geometrical optimizations are performed on these isomers with the density functional theory method. The calculated results demonstrate that the two lowest-energy isomers are Sc₂S@C₉₀:99913 and Sc₂S@C₉₀:99915, respectively. Both isomers satisfy the isolated-pentagon rule. To clarify the relative stabilities of the five lowest-energy isomers of Sc₂S@C₉₀ at high temperatures, enthalpy-entropy interplay has been taken into consideration with respect to the temperature range of up to 4000 K; the calculations demonstrate that the two lowest-energy isomers of Sc₂S@C₉₀ may coexist in the soot at high temperatures. Structural analysis demonstrated that the two isomers can transfer into each other by two Stone-Wales rotations, further suggesting the possibility of interconversion between them. Molecular orbital analysis indicates that Sc2S cluster transfers four electrons to the cage; however nature charge analysis demonstrates the charges transferred from the encaged cluster to the parent cage is much smaller than that with the simple molecular orbital analysis. The quantum theory of atoms in molecules is used to investigate the connectivity and interaction nature between the encaged cluster and parent cage. The results show that there are strong interactions between the encaged cluster and parent cage. The simulated infrared spectra of the two lowest-energy isomers are provided to assist future experimental identification and characterization of the structure of Sc₂S@C₉₀.

Key words: endohedral fullerene, Sc₂S@C₉₀, density functional theory, relative concentrations, QTAIM

引用此文

雷丹, 赵冲, 甘利华. 金属硫化物富勒烯Sc₂S@C₉₀的结构与性质[J]. 化学学报, 2014, 72(10): 1105-1109.

Lei Dan, Zhao Chong, Gan Lihua. Structures and Properties of Metal Sulfide Fullerene Sc₂S@C₉₀[J]. Acta Chimica Sinica, 2014, 72(10): 1105-1109.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] Popov, A. A.; Yang, S. Chem. Rev. 2013, 113, 5989.
[2] Akasaka, T.; Nagase, S. Endofullerenes: A New Family of Carbon Clusters, Kluwer Academic, Dordrecht, 2002, pp. 1～11.
[3] Chaur, M. N.; Melin, F.; Ortiz, A. L.; Echegoyen, L. Angew. Chem., Int. Ed. 2009, 48, 7514.
[4] Akasaka, T.; Wudl, F.; Nagase, S. Chemistry of Nanocarbons, Wiley, New York, 2010, pp. 2～3.
[5] Chai, Y.; Guo, T.; Jin, C.; Haufler, R. E.; Chibante, L. P. F.; Fure, J.; Wang, L.; Alford, J. M. J. Phys. Chem. 1991, 95, 7564.
[6] Lu, X.; Slanina, Z.; Akasaka, T.; Tsuchiya, T.; Mizorogi, N.; Nagase, S. J. Am. Chem. Soc. 2010, 132, 5896.
[7] (a) Cao, B.; Nikawa, H.; Nakahodo, T.; Tsuchiya, T.; Maeda, Y.; Akasaka, T.; Sawa, H.; Slanina, Z.; Mizorogi, N.; Nagase, S. J. Am. Chem. Soc. 2008, 130, 983.
(b) Kurihara, H.; Lu, X.; Iiduka, Y.; Mizorogi, N.; Slanina, Z.; Tsuchiya, T.; Nagase, S.; Akasaka, T. Chem. Commun. 2012, 48, 1290.
[8] (a) Krause, M.; Dunsch, L. ChemPhysChem 2004, 5, 1445.
(b) Wang, T.-S.; Chen, N.; Xiang, J.-F.; Li, B.; Wu, J.-F.; Xu, W.; Jiang, L.; Tan, K.; Shu, C.-Y.; Wang, C.-R. J. Am. Chem. Soc. 2009, 131, 16646.
[9] Shi, J.; Wang, Q.; Chen, J.; Zheng, M.; Gao, F. Acta Chim. Sinica 2011, 69, 2015. (史娟兰, 汪庆祥, 陈建平, 郑梅霞, 高飞, 化学学报, 2011, 69, 2015.)
[10] Gao, Y.-Y.; Liu, L.-H.; Ou, Z.-Z.; Li, Y.; Yang, G.-Q.; Wang, X.-S. Acta Phys.-Chim. Sin. 2010, 26, 495. (高云燕, 刘丽华, 欧植泽, 李嫕, 杨国强, 王雪松, 物理化学学报, 2010, 26, 495.)
[11] Liu, Y.; Liu, J.; Zhang, L.; Fang, J.; Zhang, W.; Liu, Z. Chin. J. Org. Chem. 2014, 34, 1021. (刘艳姣, 刘菁, 张林骅, 方俊锋, 张文俊, 刘治田, 有机化学, 2014, 34, 1021.)
[12] Yin, J.-J.; Lao, F.; Fu, P. P.; Wamer, W. G.; Zhao, Y.; Wang, P. C.;
Qiu, Y.; Sun, B.; Xing, G.; Dong, J.; Liang, X.-J.; Chen, C. Biomaterials 2009, 30, 611.
[13] Sitharaman, B.; Wilson, L. J. J. Biomed. Nanotechnol. 2007, 3, 342.
[14] Zhang, J.; Liu, K.; Xing, G.; Ren, T.; Wang, S. J. Radioanal. Nucl. Chem. 2007, 272, 605.
[15] Anilkumar, P.; Lu, F.; Cao, L.; Luo, P. G.; Liu, J.-H.; Sahu, S.; Tackett, K. N.; Wang, Y.; Sun, Y.-P. Curr. Med. Chem. 2011, 18, 2045.
[16] Dunsch, L.; Yang, S.; Zhang, L.; Svitova, A.; Oswald, S.; Popov, A. A. J. Am. Chem. Soc. 2010, 132, 5413.
[17] Chen, N.; Chaur, M. N.; Moore, C.; Pinzón, J. R.; Valencia, R.; Rodríguez-Fortea, A.; Poblet, J. M.; Echegoyen, L. Chem. Commun. 2010, 46, 4818.
[18] Mercado, B. Q.; Chen, N.; Rodríguez-Fortea, A.; Mackey, M. A.; Stevenson, S.; Echegoyen, L.; Poblet, J. M.; Olmstead, M. M.; Balch, A. L. J. Am. Chem. Soc. 2011, 133, 6752.
[19] (a) Albertazzi, E.; Domene, C.; Fowler, P. W.; Heine, T.; Seifert, G.; Alsenoy, C. V.; Zerbetto, F. Phys. Chem. Chem. Phys. 1999, 1, 2913.
(b) Campbell, E. E. B.; Fowler, P. W.; Mitchell, D.; Zerbetto, F. Chem. Phys. Lett. 1996, 250, 544.
[20] Kobayashi, K.; Nagase, S. J. Am. Chem. Soc. 1997, 119, 12693.
[21] (a) Wang, C.-R.; Kai, T.; Tomiyama, T.; Yoshida, T.; Kobayashi, Y.; Nishibori, E.; Takata, M.; Sakata, M.; Shinohara, H. Nature 2000, 408, 426.
(b) Yang, T.; Zhao, X.; Xu, Q.; Zhou, C.; He, L.; Nagase, S. J. Mater. Chem. 2011, 21, 12206.
(c) Kato, H.; Taninaka, A.; Sugal, T.; Shinohara, H. J. Am. Chem. Soc. 2003, 125, 7782.
[22] http://www.mathematik.uni-bielefeld.de/CaGe/.
[23] Fowler, P. W.; Manolopoulos, D. E. An Atlas of Fullerenes, Oxford, UK, 1995, pp. 23～41.
[24] Frisch, M. J. GAUSSIAN 09, Revision A.02, GAUSSIAN, Inc., Pittsburgh, PA, 2009.
[25] AIM2000 Home Page. http://www.aim2000.de.
[26] Yang, T.; Zhao, X.; Nagase, S. Chem. Eur. J. 2013, 19, 2649.
[27] Chen, N.; Beavers, C. M.; Mulet-Gas, M.; Rodríguez-Fortea, A.; Munoz, E. J.; Li, Y.-Y.; Olmstead, M. M.; Balch, A. L.; Poblet, J. M.; Echegoyen, L. J. Am. Chem. Soc. 2012, 134, 7851.
[28] Gan, L.-H.; Lei, D.; Zhao, C.; Guo, X. Chem. Phys. Lett. 2014, 604, 101.
[29] Gan, L.-H.; Chang, Q.; Zhao, C.; Wang, C.-R. Chem. Phys. Lett. 2013, 570, 121.
[30] Slanina, Z.; Lee, S.-L.; Uhlík, F.; Adamowicz, L.; Nagase, S. Theor. Chem. Acc. 2007, 117, 315.
[31] Stone, A. J.; Wales, D. J. Chem. Phys. Lett. 1986, 128, 501.
[32] Bader, R. F. W. Atoms in Molecules: A Quantum Theory, Oxford, 1990.
[33] Macchi, P.; Sironi, A. Coord. Chem. Rev. 2003, 383.
[34] (a) Cremer, D.; Kraka, E. Angew. Chem. 1984, 96, 612.
(b) Cremer, D.; Kraka, E. Angew. Chem. Int. Ed. Engl. 1984, 23, 627.
[35] Matta, C. F.; Boyd, R. J. The Quantum Theory of Atoms in Molecules. From Solid State to DNA and Drug Design, Wiley-VCH, Weinheim, 2007.

金属硫化物富勒烯Sc₂S@C₉₀的结构与性质

Structures and Properties of Metal Sulfide Fullerene Sc₂S@C₉₀

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

参考文献

相关文章 15

编辑推荐

相关统计

本文评价

[1]	黄广龙, 薛小松. “陈试剂”作为三氟甲基源机理的理论研究[J]. 化学学报, 2024, 82(2): 132-137.
[2]	梁雪峰, 荆剑, 冯昕, 赵勇泽, 唐新员, 何燕, 张立胜, 李慧芳. 共价有机框架COF66/COF366的电子结构: 从单体到二维平面聚合物[J]. 化学学报, 2023, 81(7): 717-724.
[3]	杨磊, 葛娇阳, 王访丽, 吴汪洋, 郑宗祥, 曹洪涛, 王洲, 冉雪芹, 解令海. 一种基于芴的大环结构的有效降低内重组能的理论研究[J]. 化学学报, 2023, 81(6): 613-619.
[4]	张少秦, 李美清, 周中军, 曲泽星. 多共振热激活延迟荧光过程的理论研究[J]. 化学学报, 2023, 81(2): 124-130.
[5]	王娟, 肖华敏, 谢丁, 郭元茹, 潘清江. 铜掺杂与氮化碳复合氧化锌材料结构和二氧化氮气体传感性质的密度泛函理论计算[J]. 化学学报, 2023, 81(11): 1493-1499.
[6]	刘金晶, 杨娜, 李莉, 魏子栋. 铂活性位空间结构调控氧还原机理的理论研究^★[J]. 化学学报, 2023, 81(11): 1478-1485.
[7]	栾雪菲, 王聪芝, 夏良树, 石伟群. 铀酰与羧酸和肟基类配体相互作用的理论研究[J]. 化学学报, 2022, 80(6): 708-713.
[8]	王珞聪, 李哲伟, 岳彩巍, 张培焕, 雷鸣, 蒲敏. 电场下偶氮苯衍生物分子顺反异构化反应机理的理论研究[J]. 化学学报, 2022, 80(6): 781-787.
[9]	王英辉, 魏思敏, 段金伟, 王康. 理论研究“受阻路易斯酸碱对”催化的烯醇硅醚氢化反应机理[J]. 化学学报, 2021, 79(9): 1164-1172.
[10]	熊昆, 陈伽瑶, 杨娜, 蒋尚坤, 李莉, 魏子栋. 理论探究水溶液条件对TMN_xC_y催化氮还原性能的增强机制[J]. 化学学报, 2021, 79(9): 1138-1145.
[11]	满清敏, 付尊蕴, 刘甜甜, 郑明月, 蒋华良. Cu催化偶联反应合成烷基芳基醚的DFT机理研究[J]. 化学学报, 2021, 79(7): 948-952.
[12]	王岩, 田英齐, 金钟, 索兵兵. 基于GPU的Hartree-Fock与密度泛函算法及程序[J]. 化学学报, 2021, 79(5): 653-657.
[13]	张丹琪, 邵英博, 郑汉良, 周碧莹, 薛小松. 双齿氮配体螯合五价碘试剂介导的苯酚氧化去芳构化机理的理论研究[J]. 化学学报, 2021, 79(11): 1394-1400.
[14]	鲁效庆, 曹守福, 魏晓飞, 李邵仁, 魏淑贤. S掺杂Fe-NC单原子催化剂氧还原机理研究[J]. 化学学报, 2020, 78(9): 1001-1006.
[15]	于沫涵, 程媛媛, 刘亚军. 萤火虫生物发光中加氧反应机理的理论研究[J]. 化学学报, 2020, 78(9): 989-993.