有机磁性体[Ni(cyclam)][Cu(tfadt)_2]及Co(N_3)(4-acetylpridine)的密度泛函研究
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摘要
本文我们用计算软件WIEN2k计算了两类非纯有机磁性材料的电子态密度和磁矩。通过计算得到的态密度,我们发现,其中有四个材料具有明显的半导体特性,有一个材料具有金属特性,这些材料都具有重要的应用价值。
计算的第一类材料是含- ( tfadt )基团非纯金属有机磁性材料[Ni(cyclam)][Cu(tfadt)2]。根据计算得到的磁矩和态密度,我们得知材料的磁性主要由Ni原子和Cu原子d轨道电子提供。化合物的总磁矩为3.000 u B,这与实验上测得的总自旋为S=3/2保持一致。同时,Ni原子和Cu原子的磁矩符号一致,说明它们之间存在着铁磁相互作用。由S原子和N原子上磁矩的大小和符号,知道化合物中铁磁耦合作用沿着链Cu-S-C-N-Ni传递,且铁磁耦合作用是通过自旋退局域化机制产生。
计算的第二类材料是:含叠氮基-(N3)不同配位基团的非纯有机磁性材料[Cu(benzoate)(N3)] n、[Cu(1-naphthoate)(N3)]n、[Cu(2-methyl-benzoate)(N3)]n和Co(N3)(4-acetylpridine)。通过第一性原理计算,发现前面三个材料是有机磁性半导体材料,第一个和第二个材料的自旋向上电子态密度与费米面相切,第三个材料的自旋向下电子态密度与费米面相切。化合物中的磁性主要由Cu原子d轨道电子提供。配体在传递化合物中铁磁耦合作用时,既有自旋退局域化机制的参与,也有自旋极化机制参与。材料中的铁磁耦合都有一条沿着链Cu-N1-Cu来传递。
最后我计算的一个材料是Co(N3)(4-acetylpridine)2,与上面四个材料不同的是,它是一个有机金属材料,而且叠氮基末端两个氮原子上的磁矩并不相等,相差近一个数量级。我们认为这主要是由于叠氮基传递铁磁耦合的方式发生了变化,以及磁性中心由Cu离子变成了Co离子。
Two kinds of non-organic magnetic material’s electronic structure and magnetic moments are calculated by the wien2k software in this article. Through the density of states calculated by the wien2k software, we find that there are four non-pure organic magnetic semiconductor materials and one organic metal material. and These materials have very important application value.
First, We calculate non-pure organic magnetic material [Ni(cyclam)][Cu(tfadt)2], according to the result, we find that the magnetic moment of this material are mainly provided by the d electron of Ni atom and Cu atom. The total magnetic moment is 3.000 u B, this is agreement with the total spin S=3/2 tested by the experiment. At the same time, the magnetic moment symbol of Ni atom and Cu atom are identical, this means that there is ferromagnetic interaction between Ni atom and Cu atom, from the magnitude and the symbol of S atom and N atom, we can see that the ferromagnetic coupling of material passes through Cu-S-C-N-Ni chain, and also from spin delocalization.
The second materials we calculated are [Cu(benzoate)(N3)] n、[Cu(1-naphthoate)(N3)]n、[Cu(2-methyl-benzoate)(N3)]n and Co(N3)(4-acetylpridine). which are organic magnetic materials. By the first principle study, the first three materials are semiconductor. and every material have one spin energy belt contacting with Fermi surface, the magnetic moment of these three non-pure organic magnets materials mainly provided by d electron of Cu atom. ferromagnetic coupling action in the material passed by ligand not only from spin delocalization but also from spin polarization, there is one route that through Cu-N1-Cu chain.
The last material we calculated is Co(N3)(4-acetylpridine)2,and it is different from the other four materials. It is an organic metal, and furthermore, magnetic moments of the end N atom on azido is not equal,but have one magnitude difference. I think the reason for it is the manner of azido passes through ferromagnetic coupling has changed, and the paramagentic center has been changed from Cu ion to Co ion.
计算的第一类材料是含- ( tfadt )基团非纯金属有机磁性材料[Ni(cyclam)][Cu(tfadt)2]。根据计算得到的磁矩和态密度,我们得知材料的磁性主要由Ni原子和Cu原子d轨道电子提供。化合物的总磁矩为3.000 u B,这与实验上测得的总自旋为S=3/2保持一致。同时,Ni原子和Cu原子的磁矩符号一致,说明它们之间存在着铁磁相互作用。由S原子和N原子上磁矩的大小和符号,知道化合物中铁磁耦合作用沿着链Cu-S-C-N-Ni传递,且铁磁耦合作用是通过自旋退局域化机制产生。
计算的第二类材料是:含叠氮基-(N3)不同配位基团的非纯有机磁性材料[Cu(benzoate)(N3)] n、[Cu(1-naphthoate)(N3)]n、[Cu(2-methyl-benzoate)(N3)]n和Co(N3)(4-acetylpridine)。通过第一性原理计算,发现前面三个材料是有机磁性半导体材料,第一个和第二个材料的自旋向上电子态密度与费米面相切,第三个材料的自旋向下电子态密度与费米面相切。化合物中的磁性主要由Cu原子d轨道电子提供。配体在传递化合物中铁磁耦合作用时,既有自旋退局域化机制的参与,也有自旋极化机制参与。材料中的铁磁耦合都有一条沿着链Cu-N1-Cu来传递。
最后我计算的一个材料是Co(N3)(4-acetylpridine)2,与上面四个材料不同的是,它是一个有机金属材料,而且叠氮基末端两个氮原子上的磁矩并不相等,相差近一个数量级。我们认为这主要是由于叠氮基传递铁磁耦合的方式发生了变化,以及磁性中心由Cu离子变成了Co离子。
Two kinds of non-organic magnetic material’s electronic structure and magnetic moments are calculated by the wien2k software in this article. Through the density of states calculated by the wien2k software, we find that there are four non-pure organic magnetic semiconductor materials and one organic metal material. and These materials have very important application value.
First, We calculate non-pure organic magnetic material [Ni(cyclam)][Cu(tfadt)2], according to the result, we find that the magnetic moment of this material are mainly provided by the d electron of Ni atom and Cu atom. The total magnetic moment is 3.000 u B, this is agreement with the total spin S=3/2 tested by the experiment. At the same time, the magnetic moment symbol of Ni atom and Cu atom are identical, this means that there is ferromagnetic interaction between Ni atom and Cu atom, from the magnitude and the symbol of S atom and N atom, we can see that the ferromagnetic coupling of material passes through Cu-S-C-N-Ni chain, and also from spin delocalization.
The second materials we calculated are [Cu(benzoate)(N3)] n、[Cu(1-naphthoate)(N3)]n、[Cu(2-methyl-benzoate)(N3)]n and Co(N3)(4-acetylpridine). which are organic magnetic materials. By the first principle study, the first three materials are semiconductor. and every material have one spin energy belt contacting with Fermi surface, the magnetic moment of these three non-pure organic magnets materials mainly provided by d electron of Cu atom. ferromagnetic coupling action in the material passed by ligand not only from spin delocalization but also from spin polarization, there is one route that through Cu-N1-Cu chain.
The last material we calculated is Co(N3)(4-acetylpridine)2,and it is different from the other four materials. It is an organic metal, and furthermore, magnetic moments of the end N atom on azido is not equal,but have one magnitude difference. I think the reason for it is the manner of azido passes through ferromagnetic coupling has changed, and the paramagentic center has been changed from Cu ion to Co ion.
引文
[1]胡安,章维益编著,“固体物理学”,高等教育出版社,2005.
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[52] Z.L.Wang, K.L.Yao, Z.l.Liu, et al., Solid State Communication 146 (2008) 412-415.
[53] L.Zhu, K.L.Yao and Z.L, Liu. J.Magn.Mater.320 (2008) L50-L54.
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[60] H.J.Xu, Z.L.Wang, K.L.Yao. J.Magn.Mater. 404 (2009) 1729-1732.
[61] Zhao-Yu Sun, Kai-Lun Yao, Wei Yao,et al. Phys.Rev.B 77,014416 (2008).
[62] Jiong-Peng Zhao,Bo-Wen Hu, E.C.Sanudo,et al. Inorg.Chem, 2009, 48:2482-2489.
[63] Xin-Yi Wang,Zhe-Ming, Wang,and Song Gao,et al. Inorg.Chem,2008,47,5720-5726.
[2]吴代鸣编著,“固体物理基础”,高等教育出版社,2007.
[3] C.基泰尔(CHARLES KITTEL)著,项金钟、吴兴惠译,“固体物理导论”化学工业出版社,2005.
[4]刘爽,孙维林,何冰晶,等.高分子通报,2004,(4):39.
[5] Naoki Shirakawa, Masafumi Tamura, Polyhedron, 2005,24:2405–2408.
[6] John R,Kirtley,Jochen Mannhart, Nature,2008,7:520-521.
[7] Jing-Lin Pang, Hong-Bin Xie, Shao-Wen Zhang,et al.,J.phys.Chem.A. 2008,112, 5251-5257.
[8] Rolf W.Berg, Anders Riisager and Rasmus Fehrmann. J.phys.Chem.A.2008 (112) 8585-8592.
[9] Yaohua Liu,Shannon M.Watson,Taegweon Lee,et a1. Phys. Rev. B 79, 075312 (2009).
[10] C.J.Ho,J.L.Her,C.P.Sun,et a1.Phys. Rev. B 76, 224417 (2007).
[11] Omar Khoumeri,Marc Montana,Thierry Terme,et a1.Tetrahedron,2008,(64): 11237 -11242
[12] Zhong-qiang Zhang, Ru-Dan Huang,Lan-Jun Dong, et al., Inorg.Chem. 362,(2009) 3056-3064.
[13] Jae-Hyuk Her,Peter W.Stephens,Jordi Ribas-Arino, et al. Inorg.Chem. 2009,48, 3296-3307.
[14] Konstantin I.Pokhodnya, Victor Dokukin and Joel S.Miller, Inorg.Chem. 2008,47, 2249-2251.
[15] Joel S.Miller,Peter K. Gantzel,Arnold L.Rheingold, et al. Inorg.Chem. 2009,48, 4201-4206.
[16] Mark D.Harvey, T.Daniel Crawford and Gordon T .Yee. Inorg.Chem. 2008, 47, 5649-5655.
[17] Jamie L.Manson, Marianne M.Conner,John A.Schlueter, et al,Chem.Mater. 2008, 20,7408-7416.
[18] Elvira M.Bauer, Carlo Bellitto,Guido Righini, et al. Inorg.Chem, 2008, 47, 10945-10952.
[19] Xiu-Teng Wang, Zhe-Ming Wang,and Song Gao. Inorg.Chem, 2007,46,10452 -10454 .
[20] Ru-Yin Li,Xin-Yi Wang,Tao Liu, et al. Inorg.Chem, 2008,47,8134-8142.
[21] Jose Suarez-Varela,Antonio J.Mota,Hakima Aouryaghal,et al. Inorg.Chem, 2008,47, 8143-8158.
[22] Oscar Fabelo,Jorge Pasan,Laura Canadillas-Delgado, et al. Inorg.Chem, 2008,47, 8143-8158.
[23] Ying-Bing Lu,Ming-Sheng Wang,Wei-Wei Zhou, et al. Inorg.Chem, 2008, 47,8935 -8942.
[24] Tadaaki Ikoma, Hiroki Oshio,Masashi Yamamoto, et al. J.phys.Chem.A 2008,112,8641-8648.
[25] Hong Deng,Yongcai Qiu,Carole Daiguebonne,et al. Inorg.Chem,2008,47, 5866 -5872.
[26]吴瑞雯,林云,林展如.科学技术与工程. 2003,3(3):1.
[27]钟昭明.磁性材料与器件. 1999 ,12.
[28]孟笑天,李永利,李保卫.生物磁学. 2006, 6(1):61.
[29] Ronny Sondjaja, T.Alan Hatton and Michael K.C.Tam. J.Magn. Mater.321 (2009) L2393-L2397.
[30] Wei-Jiang Lou, Shuang-Quan Zang, Qing-Lun,et al. Inorg. Chim . Acta362 (2009), 3005-3012.
[31] zhong-qiang Zhang, Ru-Dan Huang, Lan-Jun Dong, et al. Inorg. Chim. Acta, 362 (2009) 3056-3064.
[32] T. Itou, A.Oyamada, S.maegawa, et al., Phys. Rev. B 79, 174517 (2009).
[33] D.A.Garanin and E.M.Chudnovsky. Phys. Rev.Lett. 102, 097206 (2009).
[34] Agnes Antal, Titusz Feher,Andras Janossy, et al., Phys. Rev. Lett. 102, 086404 (2009).
[35] Youn-Seok Choi,Ki-Suk Lee,and Sang-Koog Kim. Phys. Rev. B 79, 184424(2009).
[36] N.Tsyrulin, T.Pardini, R.R.Singh, et al., Phys. Rev. Lett. 102,197201 (2009).
[37] M.N.Popova, T.N.Stanislavchuk, B.Z.Malkin,et al., Phys. Rev. Lett. 102, 87403 (2009).
[38] Hai-Zhou Lu, Bin Zhou, and Shun-Qing Shen. Phys. Rev. B 79, 174419 (2009).
[39] J.J.Henderson, C.M.Ramsey, E.del Barco,et al., Phys. Rev. B 78,214413 (2008).
[40] K.Bernot, J.Luzon, A.Caneschi, D.Gatteschi,et al., Phys. Rev. B 79,134419 (2008).
[41] J.B.Kortright,D.M.Lincoln,Rshima Edelstein,et al., Phys. Rev. Lett. 100, 257204 (2008).
[42] Mircea Trif, Filippo Troiani, Dimitrije Stepanenko,et al Phys. Rev. Lett. 101, 217201 (2008).
[43] Dongping Liu, Yi.bin Hu, Hong Guo,et al., Phys. Rev. B 78,193307 (2008).
[44] P.Blaha,K.Schwarz,G.K.H.Madsen,et al. 2001 ISBN 3-9501031-1-2
[45] Olivier Jeannin, Rodolphe Clerac, Thomas Cauchy, et al. Inorg.Chem,2008, 47, 10656 -10661.
[46] W.D. Zou, Z.L.Liu, K.L. Yao, J.Magn. Mater.263 (2003) 360-365.
[47] K.L.Yao, J.Zhang, Z.L.Liu, et al. Physics B 398 (2007) 40-45
[48] Wei-Wwi Sun, Xiong-Bing Qian, Chun-Yan Tian, , et al. Inorganica Chimica Acta 362 (2009) 2744-2748
[49] H.H.Fu, K.L.Yao, and Z.L.Liu. Phys.Rev.B 77,219901 (2008).
[50] K.L.Yao, Q.M.Liu, and Z.L.Liu. Phys.Rev.B 70,224430 (2004)
[51] S.J.Luo and K.L.Yao. Phys.Rev.B 67,214429 (2003).
[52] Z.L.Wang, K.L.Yao, Z.l.Liu, et al., Solid State Communication 146 (2008) 412-415.
[53] L.Zhu, K.L.Yao and Z.L, Liu. J.Magn.Mater.320 (2008) L50-L54.
[54] Z.B.Li, K.L.Yao, and Li Liu. J.Magn.Mater. 320 (2008) 1759-1764
[55] H.M.Huang, et al.,J.Magn.Mater. (2009). 2200-2203
[56] K.L.Yao,Z.B.Li,Z.L.Liu. J.Magn.Mater. 320 (2008) 222-226.
[57] K.L.Yao,Z.W.Wang,Z.L.Liu, et al.J.Magn.Mater. 320 (2008) 2074-2077.
[58] H.J.Xu,Z.L.Wang,and K.L.Yao. physics B 404 (2009) 1729-1732.
[59] H.H.Fu, K.L.Yao, and Z. L. Liu. Phys.Rev.B 73,104454 (2006).
[60] H.J.Xu, Z.L.Wang, K.L.Yao. J.Magn.Mater. 404 (2009) 1729-1732.
[61] Zhao-Yu Sun, Kai-Lun Yao, Wei Yao,et al. Phys.Rev.B 77,014416 (2008).
[62] Jiong-Peng Zhao,Bo-Wen Hu, E.C.Sanudo,et al. Inorg.Chem, 2009, 48:2482-2489.
[63] Xin-Yi Wang,Zhe-Ming, Wang,and Song Gao,et al. Inorg.Chem,2008,47,5720-5726.