Differential Many-Body Cooperativity in Electronic Spectra of Oligonuclear Transition-Metal Complexes
Differential Many-Body Cooperativity in Electronic Spectra of Oligonuclear Transition-Metal Complexes
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DOI：
10.1002/cphc.201500626
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发表时间：
2016-01-04
期刊：
影响因子：
2.9
通讯作者：
Klopper, Wim
中科院分区：
文献类型：
--
作者：
Chmela, Jiri;Harding, Michael E.;Klopper, Wim
在计算化学中，非加性和协同效应可以用能量的（微分）多体展开或所关注分子系统的任何其他物理性质来定义。单体项描述子系统的能量或性质，二体项描述非加性但成对的贡献，三体项以及高阶项可以被解释为协同性的度量。在本文中，这一概念被应用到同三核过渡金属配合物的紫外/可见（UV/维斯）光谱的分析，通过多体展开的光谱变化引起的三个过渡金属离子中的每一个被另一个过渡金属离子取代，以产生不同的同三核过渡金属配合物。通过计算三角形配合物[M-3{Si（mt（Me））（3）}（2）]（M=Pd/Pt，mt（Me）=甲巯咪唑）和三配位的三苯乙炔基氮杂环卡宾Rh/Ir配合物的光谱，说明了这一概念，分别显示出大的和小的微分三体协同效应.
In computational chemistry, non-additive and cooperative effects can be defined in terms of a (differential) many-body expansion of the energy or any other physical property of the molecular system of interest. One-body terms describe energies or properties of the subsystems, two-body terms describe non-additive but pairwise contributions and three-body as well as higher-order terms can be interpreted as a measure for cooperativity. In the present article, this concept is applied to the analysis of ultraviolet/visible (UV/Vis) spectra of homotrinuclear transition-metal complexes by means of a many-body expansion of the change in the spectrum induced by replacing each of the three transition-metal ions by another transition-metal ion to yield a different homotrinuclear transition-metal complex. Computed spectra for the triangulo-complexes [M-3{Si(mt(Me))(3)}(2)] (M=Pd/Pt, mt(Me)=methimazole) and tritopic triphenylene-based N-heterocyclic carbene Rh/Ir complexes illustrate the concept, showing large and small differential three-body cooperativity, respectively.