Spin-orbit coupling and d2-d2 interactions in dinuclear bioctahedral metal clusters

被引:2
作者
Kozlova, Svetlana G. [1 ,2 ]
Ryzhikov, Maxim R. [1 ]
Slepkov, Vladimir A. [1 ]
Gabuda, Svyatoslav P. [1 ]
机构
[1] Russian Acad Sci, Nikolaev Inst Inorgan Chem, Siberian Branch, Novosibirsk, Russia
[2] Novosibirsk State Univ, Novosibirsk 630090, Russia
基金
俄罗斯基础研究基金会;
关键词
Spin-orbital interaction; Bifurcations; Dinuclear bioctahedral face-shared cluster; complexes; Magnetism; EXPERIMENTAL ELECTRON-DENSITY; MOLECULAR-STRUCTURES; MAGNETIC-PROPERTIES; TRANSITION; ENERGY; APPROXIMATION; DIMER; SYSTEMS; STATE; SE;
D O I
10.1016/j.poly.2013.12.013
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The electronic structure and the metal-metal d(2)-d(2) interactions in dinuclear bioctahedral face-shared cluster complexes [M2X9](3)- (M = V, Nb, Ta, and X = Cl, Br, I) have been studied with OFT and topological methods QTAIM and ELF. The ground states of the complexes are shown to be spin-paired and nonmagnetic only in the approximation of spin-orbit interaction. The result correlates well with experimental data on magnetic susceptibility for solid-state complexes containing [Nb2X9](3)- and [Ta2X9](3-) anions as well as for [V2X9](3-) anions in low-temperature spin-paired modifications of Cs3V2Cl9 and Rb3V2Br9 complexes. The transition to the high-temperature spin-paramagnetic state of [V2X9](3-) anions is shown to be related to the bifurcation of d(2)-d(2) interaction at some critical distance D-CR(M-M) and to weakening of spin-orbit coupling in divanadium complexes. (C) 2013 Elsevier Ltd. All rights reserved.
引用
收藏
页码:59 / 64
页数:6
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