Differential Many‐Body Cooperativity in Electronic Spectra of Oligonuclear Transition‐Metal Complexes |
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| Authors: | Jiří Chmela Dr. Michael E. Harding Dr. Dimitri Matioszek Dr. Christopher E. Anson Prof. Dr. Frank Breher Prof. Dr. Wim Klopper |
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| Affiliation: | 1. Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany;2. Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen, Germany;3. Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany |
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| Abstract: | ![]()
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 [M3{Si(mtMe)3}2] (M=Pd/Pt, mtMe=methimazole) and tritopic triphenylene‐based N‐heterocyclic carbene Rh/Ir complexes illustrate the concept, showing large and small differential three‐body cooperativity, respectively. |
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| Keywords: | carbene complexes cooperativity electronic spectra many-body expansions non-additivity |
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