团簇Ni_3CoP电子性质与磁性研究
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摘要
设计团簇Ni_3CoP模型对非晶态合金Ni-Co-P进行局域结构的模拟,基于密度泛函理论(DFT)并在B3LYP/Lanl2dz水平下运用Gaussian 09程序对其进行结构优化以及有关电子性质与磁性的计算,对所得到的理论数据进行分析.结果表明:团簇Ni_3CoP费米能级左侧的最高峰由Ni-d、Co-d、P-p共振产生,形成了d-d-p杂化的成键轨道,并主要由Ni-d轨道贡献;对于团簇Ni_3CoP内部的电子转移,以P原子提供电子的能力最强,Co原子次之,Ni原子则整体以接受电子为主.团簇Ni_3CoP 3重态下的构型具有磁性,且Ni原子磁矩对团簇总磁矩的贡献较大.分析d轨道的电子自旋态密度图,发现其对称性最不好,这说明其上的成单电子最多,是团簇磁性的主要来源.同时,研究还发现p轨道对团簇磁性的贡献同样不可忽略.
Cluster Ni_3CoP is designed to simulate the partial structure of amorphous alloy Ni-Co-P.The cluster′s structure is optimized under B3 LYP/Lanl2 dz level based on the Density Functional Theory and some data about its electronic and magnetic properties are obtained in the Gaussian09 program.By analyzing all these theoretical data,the results follow that the peak on the left of E_F is formed by the resonance of Ni-d,Co-d,P-p,which leads to the formation of a d-d-p hybridization bonding orbital and it mainly consists of Ni-d.As for the electronic transfer inside cluster Ni_3CoP,P shows the best ability to provide electrons compared with Co,but Ni tends to accept electrons.Configurations in triplet are magnetic and the total magnetic moment is mainly originated from Ni.Density of state of d orbital shows that its worst symmetry symbolizes massive unpaired electrons in it so d orbital contributes the most to cluster Ni_3CoP′s magnetism.Simultaneously,p orbital′s contribution to the cluster′s magnetism can not be overlooked either.
Cluster Ni_3CoP is designed to simulate the partial structure of amorphous alloy Ni-Co-P.The cluster′s structure is optimized under B3 LYP/Lanl2 dz level based on the Density Functional Theory and some data about its electronic and magnetic properties are obtained in the Gaussian09 program.By analyzing all these theoretical data,the results follow that the peak on the left of E_F is formed by the resonance of Ni-d,Co-d,P-p,which leads to the formation of a d-d-p hybridization bonding orbital and it mainly consists of Ni-d.As for the electronic transfer inside cluster Ni_3CoP,P shows the best ability to provide electrons compared with Co,but Ni tends to accept electrons.Configurations in triplet are magnetic and the total magnetic moment is mainly originated from Ni.Density of state of d orbital shows that its worst symmetry symbolizes massive unpaired electrons in it so d orbital contributes the most to cluster Ni_3CoP′s magnetism.Simultaneously,p orbital′s contribution to the cluster′s magnetism can not be overlooked either.
引文
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[2] Zhang Yanghuan,Wang Pengpeng,Bu Wengang,et al.Improved hydrogen storage kinetics of nanocrystalline and amorphous Ce-Mg-Ni-based CeMg 12-type alloys synthesized by mechanical milling [J].RSC Advances,2018,8(41):23353-23363.
[3] Kang Min,Zhang Yin,Li Hengzheng.Study on the performances of Ni-Co-P/BN(h) nanocomposite coatings made by jet electrodeposition [J].Procedia CIRP,2018,68:221-226.
[4] Li Baosong,Zhang Weiwei.Electrochemical deposition of Ni-Co/SiC nanocomposite coatings for marine environment [J].International Journal of Electrochemical Science,2017,12(8):7017-7030.
[5] Sharma S,Sharma S,Sharma A,et al.Co-deposition of synthesized ZnO nanoparticles into Ni-P matrix using electroless technique and their corrosion study [J].Journal of Materials Engineering and Performance,2016,25(10):4383-4393.
[6] Sathishkumar A,Kumar M A,Prabu D V,et al.Investigation of wear behaviour properties of electroless Ni-Co-P ternary alloy coating [J].International Journal of Scientific Research in Science,Engineering and Technology,2017,3(1):16-22.
[7] Feng Yi,Yu Xinyao,Paik U.Nickel cobalt phosphides quasi-hollow nanocubes as an efficient electrocatalyst for hydrogen evolution in alkaline solution [J].Chemical Communications,2016,52(8):1633-1636.
[8] Li Junzhi,Wei Guodong,Zhu Yukun,et al.Hierarchical NiCoP nanocone arrays supported on Ni foam as an efficient and stable bifunctional electrocatalyst for overall water splitting [J].Journal of Materials Chemistry A,2017,5(28):14828-837.
[9] Hou Chunchao,Li Qiang,Wang Chuanjun,et al.Ternary Ni-Co-P nanoparticles as noble-metal-free catalysts to boost the hydrolytic dehydrogenation of ammonia-borane [J].Energy and Environmental Science,2017,10(8):1770-1776.
[10] Hu Enlai,Feng Yafei,Nai Jianwei,et al.Construction of hierarchical Ni-Co-P hollow nanobricks with oriented nanosheets for efficient overall water splitting [J].Energy and Environmental Science,2018,11(4):872-880.
[11] Qin Zhixiao,Chen Yubin,Huang Zhenxiong,et al.A bifunctional NiCoP-based core/shell cocatalyst to promote separate photocatalytic hydrogen and oxygen generation over graphitic carbon nitride [J].Journal of Materials Chemistry A,2017,5(36):19025-19035.
[12] Pan Yuan,Chen Yinjuan,Lin Yan,et al.Cobalt nickel phosphide nanoparticles decorated carbon nanotubes as advanced hybrid catalysts for hydrogen evolution [J].Journal of Materials Chemistry A,2016,4(38):14675-14686.
[13] Yuan Jing,Wang Jihui,Gao Yun,et al.Preparation and magnetic properties of Ni-Co-P-Ce coating by electroless plating on silicon substrate [J].Thin Solid Films,2017,632:1-9.
[14] El-Sayed A H,Hemeda O M,Tawfik A,et al.Superior values of the initial permeability for electrodeposited Ni-Co-P-BaFe12O19 composite films [J].Phase Transitions,2017,90(4):325-334.
[15] Gao Yun,Wang Jihui,Yuan Jing,et al.Preparation and magnetic properties of Ni-P-La coating by electroless plating on silicon substrate [J].Applied Surface Science,2016(364):740-746.
[16] Wu Chun,Wang Kai,Li Donggang,et al.Tuning microstructure and magnetic properties of electrodeposited CoNiP films by high magnetic field annealing [J].Journal of Magnetism and Magnetic Materials,2016,416:61-65.
[17] Bi Siyi,Zhao Hang,Hou Lei,et al.Enhanced electromagnetic interference shielding effects of Cobalt-Nickel polyalloy coated fabrics with assistance of rare earth elements [J].Fibers and Polymers,2018,19(5):1084-1093.
[18] Yu Xuegang.Hyperbolic multi-topology and the basic principle in quantum mechanics [J].Advances in Applied Clifford Algebras,1999,9(1):109-118.
[19] Beck A.Density-functional thermochemistry.III.The role of exact exchange [J].The Journal of Chemical Physics,1993,98(7):5648-5652.
[20] Hay P J,Wadt W R.Ab initio effective core potentials for molecular calculations [J].The Journal of Chemical Physics,1985,82(1):299-310.
[21] Fang Zhigang,Hu Hongzhi,Guo Jingxue.Quantum chemical study on geometry and property of cluster Ni4P [J].Chinese Journal of Structural Chemistry,2006,25(1):7-16.
[22] Lu Tian,Chen Feiwu.Multiwfn:a multifunctional wavefunction analyzer [J].Journal of Computational Chemistry,2012,33(5):580-592.
[23] Fukui K,Yonezawa T,Shingu H.A molecular orbital theory of reactivity in aromatic hydrocarbons [J].Journal of Chemical Physics,1952,20(10):1653-1653.
[24] 徐诗浩,方志刚,韩建铭,等.团簇V3B2成键及磁学性质研究 [J].广西师范大学学报:自然科学版,2017,35(3):89-96.