密度泛函理论在分子磁学中的应用2.混合桥联三核镍配合物自旋交换作用

化学学报 ›› 2004, Vol. 62 ›› Issue (20): 1973-1980. 下一篇

研究论文

密度泛函理论在分子磁学中的应用2.混合桥联三核镍配合物自旋交换作用

胡宗超^1,2, 卫海燕¹, 王凡¹, 赵琦华^1,3, 陈志达¹

1. 北京大学化学与分子工程学院, 稀土材料化学及应用国家重点实验室, 北京, 100871;
2. 贵州大学化学系, 贵阳, 550025;
3. 云南大学化学系, 昆明, 650091

投稿日期:2004-04-16 修回日期:2004-06-25 发布日期:2014-02-17
通讯作者: 陈志达,E-mail:zdchen@pku.edu.cn E-mail:zdchen@pku.edu.cn
基金资助:
国家自然科学基金(Nos.20273005,20318001)、教育部博士点基金(No.20030001066)资助项目.

Application of Density Functional Theory to Molecular Magnetism 2. Magnetic Coupling Interaction in Mixed Bridged Trinuclear Nickel Complexes

HU Zhong-Cao^1,2, WEI Hai-Yan¹, WANG Fan¹, ZHAO Qi-Hua^1,3, CHEN Zhi-Da¹

1. Department of Chemistry, State Key Laboratory of Rare Earth Materials Chemistry and Applications, Peking University, Beijing 100871;
2. Department of Chemistry, Guizhou University, Guiyang 550025;
3. Department of Chemistry, Yunnan University, Kunming 650091

Received:2004-04-16 Revised:2004-06-25 Published:2014-02-17

文章分享

摘要/Abstract

用密度泛函理论结合对称性破损方法(DFT-BS)研究了混合桥联三核镍配合物的磁交换耦合作用.这类化合物是由三唑和异硫氰酸根桥联形成的混合桥配合物.计算表明,在标题化合物中,三唑桥传递反铁磁耦合作用,而异硫氰酸根桥传递铁磁耦合作用;并且,随着异硫氰酸根取代三唑桥的数目增加,配合物的铁磁作用增强,在一定意义上说明了混合桥磁耦合作用的加合性.Mulliken自旋布居分析表明,无论是三唑桥还是异硫氰酸根桥,它们的磁交换作用机理都是磁中心的自旋离域.分子磁轨道分析显示,对于三唑桥,在局域磁轨道之间存在着强的轨道作用,导致了反铁磁耦合;对于异硫氰酸根桥,局域磁轨道之间弱的相互作用,表现了铁磁耦合作用.对标题化合物的研究说明了DFT-BS方法可用于三核体系磁交换作用的研究.

关键词: 密度泛函理论, 对称性破损方法, 分子磁性, 自旋超交换, 三核Ni(Ⅱ)

Calculations on the magnetic coupling interaction in the mixed bridged trinuclear nickel complexes with triazole and isothiocyanate bridge ligands have been carried out by using the density functional theory combined with the broken symmetry approach (DFT-BS). It is found that in the title complexes the coupling interaction of the triazole bridge is antiferromagnetic while the isothiocyanate bridge transfers a ferromagnetic coupling. As increasing the number of isothiocyanate bridge the ferromagnetic characteristic is enhanced. The Mulliken population analyses show that in the title complexes there is a spin delocalization mechanism of magnetic coupling through the bridges. From molecular magnetic orbitals, it is shown that there is a stronger orbital interaction among the local magnetic orbitals through the triazole bridge, while isothiocyanate bridge gives rise to a weaker orbital interaction among the local magnetic orbitals. It is important to note that the DFT-BS suitable to the transition metal binuclear complexes can be also applied to magnetic exchange interaction for the transition metal trinuclear complexes.

Key words: density functional theory, broken symmetry approach, molecular magnetism, superexchange interaction, trinuclear nickel complex

引用此文

胡宗超, 卫海燕, 王凡, 赵琦华, 陈志达. 密度泛函理论在分子磁学中的应用2.混合桥联三核镍配合物自旋交换作用[J]. 化学学报, 2004, 62(20): 1973-1980.

HU Zhong-Cao, WEI Hai-Yan, WANG Fan, ZHAO Qi-Hua, CHEN Zhi-Da. Application of Density Functional Theory to Molecular Magnetism 2. Magnetic Coupling Interaction in Mixed Bridged Trinuclear Nickel Complexes [J]. Acta Chimica Sinica, 2004, 62(20): 1973-1980.

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

分享此文

参考文献

[1] Ruiz, E.; Cano, J.; Alvarez, S.; Alemany, P. J. Am.Chem. Soc. 1998, 120, 11122.
[2] Duggan, D. M.; Hendrickson, D. N. Inorg. Chem. 1974, 13,2929.
[3] Monfort, M.; Ribas, J.; Solans, X. Inorg. Chem. 1994, 33,4271.
[4] Ribas, J.; Escuer, A.; Monfort, M.; Vicente, R.; Cortes,R.; Lezama, L.; Rojo, T. Coord. Chem. Rev. 1999, 193 ～195, 1027.
[5] Iwamura, H.; Inoue, K.; Hayamizu, T. Pure Appl. Chem.1996, 68, 233.
[6] Antolini, L.; Fabretti, A. C.; Gatteschi, D.; Giusti, A.;Sessoli, R. Inorg. Chem. 1990, 29, 143.
[7] Garcia, Y.; van Köningsbruggen, P. J.; Bravic, G.;Guionneau, P.; Chasseau, D.; Cascarano, G. L.; Moscovici,J.; Lambert, K.; Michalowicz, A.; Kahn, O. Inorg. Chem.1997, 36, 6357.
[8] Thomann, M.; Kahn, O.; Guilhem, J.; Varreta, F. Inorg.Chem. 1994, 33, 6029.
[9] Keij, F. S.; de Graaff, R. A. G.; Haasnoot, J. G.; Reedijk,J. J. Chem. Soc., Dalton Trans. 1984, 2093.
[10] Van Köningsbruggen, P. J.; Gluth, M. W.; Ksenofontov, V.;Walcher, D.; Schollmeyer, D.; Levchenko, G.; Gutlich, P.Inorg. Chim. Acta 1998, 273, 54.
[11] Ribas, J.; Monfort, J. M.; Diaz, C.; Bastos, C.; Solanslb,X Inorg. Chem. 1994, 33,484.
[12] Chaudhuri, P.; Weyhermuller, T.; Bill, E.; Wieghardt, K.Inorg. Chim. Acta 1996, 252, 195.
[13] (a) Shvelashvili, A. E.; Porai-Koshits, M. A.; Antsyshkina,A. S. J. Struct. Chem. USSR 1969, 10, 552.
(b) Ginsberg, A. P.; Martin, R. L.; Brookes, R. W.; Sherwood, R. C. Inorg. Chem. 1972, 11, 2884.
[14] (a) Vicente, R.; Escuer, A.; Ribas, J.; Solans, X. J.Chem. Soc., Dalton Trans. 1994, 259.
(b) Monfort, M.; Bastos, C.; Diaz, C.; Ribas, J.; Solans, X.Inorg. Chim. Acta 1994, 218, 185.
(c) Escuer, A.; Kumar, S. B.; Mautner, F.; Vicente, R. Inorg. Chim. Acta 1998, 269, 313.
[15] Adam, K. R.; Leong, A. L.; Lindoy, L. F.; McCool, B. J.;Ekstrom, A.; Liepa, I.; Harding, P. A.; Henrick, K.;McPartlin, M.; Tasker, P. A. J. Chem. Soc., Dalton Trans.1987, 2537.
[16] Zhao, Q.-H.; Li, H.-F.; Chen, Z.-D.; Fang, R. Inorg.Chim. Acta 2002, 336, 142.
[17] van Albada, G. A.; de Graaff, R. A. G.; Haasnoot, J. G.;Reedijk, J. Inorg. Chem. 1984, 23, 1404.
[18] Noodleman, L. J. Chem. Phys. 1981, 74, 5737.
[19] Noodleman, L.; Baerends, E. J. J. Am. Chem. Soc. 1984,106, 2316.
[20] Noodleman, L.; Case, D. A. Adv. Inorg. Chem. 1992, 38,423.
[21] Li, J.; Noodleman, L.; Case, D. A. In Inorganic Electronic Structure and Spectroscopy, Vol. 1, Eds.: Solomon, E. I.;Lever, A. B. P., Wiley, New York, 1999, p. 661.
[22] Ruiz, E.; Alemany, P.; Alvarez, S.; Cano, J. J. Am. Chem.Soc. 1997, 119, 1297.
[23] Ruiz, E.; Alemany, P.; Alvarez, S.; Cano, J. Inorg. Chem.1997, 36, 3683.
[24] Yan, F.; Chen, Z.-D. J. Phys. Chem. A 2000, 104, 6295.
[25] Adamo, C.; Barone, V.; Bencini, A.; Totti, F.; Ciofini, I.Inorg. Chem. 1999, 38, 1996.
[26] Chen, Z.-D.; Xu, Z.-T.; Zhang, L.; Yan, F.; Lin, Z.-Y.J. Phys. Chem. A 2001, 105, 9710.
[27] Zhang, L.; Chen, Z.-D. Chem. Phys. Lett. 2001, 345, 353.
[28] Ren, J.; Chen, Z.-D. Acta Chim. Sinica 2003, 61, 1537 (in Chinese).(任杰, 陈志达, 化学学报, 2003, 61, 1537.)
[29] Amsterdam Density Functional (ADF), version 2003.02, Scientific Computing and Modelling, Theoretical Chemistry, Virje Universiteit, Amsterdam, The Netherlands, 2003.
[30] Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980,58, 1200.
[31] Becke, A. D. Phys. Rev. A 1988, 38, 3098.
[32] Perdew, J. P.; Wang, Y. Phys. Rev. B 1988, 33, 8800.
[33] (a) Boerrigter, P. M.; Velde, G. T.; Baerends, E. J. Int. J.Quantum Chem. 1988, 33, 87.
(b) Velde, G. T.; Baelends, E. J. J. Comput. Phys. 1992,99,84.
[34] (a) Snijders, J. G.; Baerends, E. J. Mol. Phys. 1978, 36,1789.
(b) Snijders, J. G.; Baerends, E. J.; Ros, P. Mol. Phys.1979, 38, 1909.
(c) Ziegler, T.; Snijders, J. G.; Baerends, E. J. J. Chem.Phys. 1981, 74, 1271.
[35] Ruiz, E.; Cano, J.; Alvarez, S.; Alemany, P. J. Comput.Chem. 1999, 20, 1391.
[36] Ren, Q.-H.; Chen, Z.-D.; Ren, J.; Wei, H.-Y.; Feng,W.-T.; Zhang, L. J. Phys. Chem. A 2002, 106, 6161.
[37] Ginsberg, A. P.; Martin, R. L.; Sherwood, R. C. Inorg.Chem. 1968, 7, 932.
[38] Arriortua, M. I.; Cortes, A. R.; Lezama, L.; Rojo, T.;Solans, X.; Font-Bardia, M. Inorg. Chem. Acta 1990, 174,263.
[39] Ribas, J.; Monfort, J. M.; Diaz, C.; Bastos, C.; Solans, X.Inorg. Chem. 1994, 33,484.
[40] Vicente, R.; Escuer, A.; Ribas, J.; Sallah el Fallah, M.;Solans, X.; Font-Bardya, M. Inorg. Chem. 1993, 32, 1920.
[41] Chaudhuri, P.; Weyhermuller, T.; Bill, E.; Wieghardt, K.Inorg. Chim. Acta 1996, 252, 195.
[42] Ribas, J.; Monfort, M.; Diaz, C.; Bastos, C.; Solans, X.Inorg. Chem. 1994, 33,484.
[43] Ribas, J.; Monfort, M.; Diaz, C.; Bastos, C.; Mer, C.;Solans, X. Inorg. Chem. 1995, 34, 4986.
[44] Ribas, J.; Escuer, A.; Monfort, M.; Vicente, R.; Cortes,R.; Lezama, L.; Rojo, T.; Goher, M. S. In Magnetism:Molecules to Materials Ⅱ, Eds: Miller, J. S.; Drillon, M.,Wiley VCH, New York, 2001, p. 307.
[45] Aebersold, M. A.; Gillon, B.; Plantevin, O.; Pardi, L.;Kahn, O.; Bergerat, P.; Seggern, I. V.; Tuczek, F.;ÖhrstrÖm, L.; Grand, A.; Lelièvre-Berna, E. J. Am. Chem.Soc. 1998, 120, 5238.
[46] Hay, P. J.; Thibeault, J. C.; Hoffmann, R. J. Am. Chem.Soc. 1975, 97, 4884.

密度泛函理论在分子磁学中的应用2.混合桥联三核镍配合物自旋交换作用

Application of Density Functional Theory to Molecular Magnetism 2. Magnetic Coupling Interaction in Mixed Bridged Trinuclear Nickel Complexes

PDF

可视化

被引次数

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]	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.
[10]	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.
[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]	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.
[15]	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.