Magnetic excitations in polyoxometalate clusters observed by inelastic neutron scattering:: Evidence for ferromagnetic exchange interactions and spin anisotropy in the tetrameric nickel(II) cluster [Ni4(H2O)2(PW9O34)2]10- and comparison with the magnetic properties

被引:80
作者
Clemente-Juan, JM
Andres, H
Borrás-Almenar, JJ
Coronado, E
Güdel, HU
Aebersold, M
Kearly, G
Büttner, H
Zolliker, M
机构
[1] Univ Valencia, Dept Quim Inorgan, E-46100 Burjassot, Spain
[2] Univ Bern, Dept Chem & Biochem, CH-3000 Bern 9, Switzerland
[3] Inst Max Von Laue Paul Langevin, F-38042 Grenoble 9, France
[4] ETH Zurich, Lab Neutronenstreuung, CH-5232 Villigen, Switzerland
[5] PSI Villigen, CH-5232 Villigen, Switzerland
关键词
D O I
10.1021/ja990197z
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The ground-state properties of the tetranuclear Ni2+ cluster [Ni-4(H2O)2(PW9O34)(2)](10-) were investigated by combining magnetic susceptibility and magnetization measurements with a detailed inelastic neutron scattering (INS) study on a fully deuterated sample of K6Na4[Ni-4(H2O)(2)(PW9O34)(2)]. 24H(2)O. The temperature dependence of the magnetic susceptibility indicates a ferromagnetic coupling of the four constituent Ni2+ ions (s = 1), and a low-temperature magnetization study provides the magnitude of the S = 4 ground-multiplet splitting due to the single-ion anisotropy of the Ni2+ ions. Besides a more direct and precise determination of the anisotropic S = 4 ground-multiplet splitting, INS enabled the determination of excited spin multiplets. The best fit to the experimental energy level diagram was obtained by an isotropic Spin Hamiltonian with the inclusion of axial single-ion anisotropy: H=-2J(S1S3 + S1S4 + S2S3 + S2S4)-2J' S1S2 + D(S-z1(2) + S-z2(2)), where J = 0.83 meV, J' = 0.39 meV, D = 0.47 meV, and D' = 0.60 meV. Within this model the experimental intensities of the magnetic cluster excitations, their characteristic dependence on the scattering vector (Q) over right arrow, as well as the temperature dependence of the magnetic susceptibility and the magnetization properties are reproduced.
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页码:10021 / 10027
页数:7
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