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Differential Many‐Body Cooperativity in Electronic Spectra of Oligonuclear Transition‐Metal Complexes
Author(s) -
Chmela Jiří,
Harding Michael E.,
Matioszek Dimitri,
Anson Christopher E.,
Breher Frank,
Klopper Wim
Publication year - 2016
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201500626
Subject(s) - cooperativity , chemistry , transition metal , spectral line , triphenylene , crystallography , chemical physics , computational chemistry , molecule , physics , quantum mechanics , organic chemistry , catalysis , biochemistry
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.