Mechanism of phase transitions affecting intramolecular electron transfer in trinuclear mixed‐valence transition‐metal compounds
Mechanism of phase transitions affecting intramolecular electron transfer in trinuclear mixed‐valence transition‐metal compounds
复制标题
三核混合价过渡金属化合物中相变影响分子内电子转移的机制
DOI：
10.1063/1.451050
复制
发表时间：
1986
影响因子：
4.4
通讯作者：
Seung M Oh
中科院分区：
文献类型：
--
作者：
T. Kambara;D. Hendrickson;M. Sorai;Seung M Oh
凝聚相中离散混合价过渡金属络合物的分子内电子离域不仅取决于单个络合物的电子结构，而且还敏感地取决于堆积排列的细节[D. N.亨德里克森，S。M. T-Y董氏T. Kambara，M. J. Cohn和M. F.摩尔，评论Inorg.Chem.4，329（1985）]。从理论上研究了固态混合价配合物的协同性质如何依赖于单个配合物中的电子定域和/或离域的问题。引入了一种唯象的分子间相互作用，它取决于电子局域化引起的分子扭曲的方向和大小。基于分子场理论建立了一个理论模型，以说明在三核混合价化合物中与电子离域有关的相变类型是可能的，以及组成分子的电子结构如何决定相变类型。
Intramolecular electron delocalization in discrete mixed‐valence transition metal complexes in the condensed phase depends not only on the electronic structure of a single complex but also sensitively on the details of the packing arrangement [D. N. Hendrickson, S. M. Oh, T.‐Y. Dong, T. Kambara, M. J. Cohn, and M. F. Moore, Comments Inorg. Chem. 4, 329 (1985)]. The problem of how the cooperative properties of mixed‐valence complexes in the solid state depend on the electron localization and/or delocalization in a single complex is studied theoretically. A phenomenological intermolecular interaction which depends on the sense and the magnitude of molecular distortion arising from the electron localization is introduced. A theoretical model is developed based on molecular field theory in order to show what types of phase transitions relating to the electron delocalization are possible in the trinuclear mixed‐valence compounds and how the electronic structure of constituent molecules determines the type of p...