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

来源：

POLYHEDRON | 2014年 / 70卷

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

页码：59 / 64

页数：6

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