Density functional study of magnetic exchange of dinuclear manganese complexes with the heteropolymolyanion: [MnⅡ2(Xn+Mo9O33)2(n-10)-(X = PⅤ, AsⅤ, SeⅥ)

• 来源期刊: 中国科学B辑（英文版）
• 年，卷（期）: 2008,（12）
• 页码范围: 1174-1181
• 页数: 8页
• 语种: 英文
• DOI: 10.1007/s11426-008-0123-3

摘要

The magnetic exchange interactions between the dimanganese(Ⅱ)-substituted complexes and the het-eropolymolyanion, [MnⅡ2(Xn+Mo9O33)2(n-10)-(X = PⅤ(Ⅰ), AsⅤ(Ⅱ), and SeⅥ(Ⅲ)), are investigated by using density functional theory combined with broken-symmetry approach (DFT-BS) method. The calculated magnetic exchange coupling constant (J) of complex Ⅱ is in reasonable agreement with the responding experimental value and the negative J values indicate that antiferromagnetic exchange interactions exist in these complexes. Furthermore, the influence of the central heteroatom on the exchange cou-pling within the dimanganese core unit is studied from standpoints of geometry, spin density and fron-tier orbitals. It demonstrates that the change of the heteroatom X via pV-AsV-SeW elongates the dis-exchange pathways, consequently, decreasing the magnitude of the antiferromagnetic coupling con-stant, J, of these species.