Ground and Excited State Properties and Vibronic Coupling Analysis of the Creutz−Taube Ion, [(NH3)5Ru-pyrazine-Ru(NH3)5]5+, Using DFT

Autor:	Alessandro Bencini, and Claude A. Daul, Ilaria Ciofini, Alessandro Ferretti
Rok vydání:	1999
Předmět:	Pyrazine Chemistry Antisymmetric relation General Chemistry Electronic structure Electron Biochemistry Catalysis Ion Vibronic coupling chemistry.chemical_compound Colloid and Surface Chemistry Excited state Density functional theory Atomic physics
Zdroj:	Journal of the American Chemical Society. 121:11418-11424
ISSN:	1520-5126 0002-7863
DOI:	10.1021/ja9920258
Popis:	In this paper we analyze using Density Functional Theory (DFT) the electronic structure of the Creutz−Taube ion, [(NH3)5Ru-pyrazine-Ru(NH3)5]5+, a classical example of a mixed-valence complex. A complete structural and bonding analysis, description of the low-lying excited states, and a vibronic coupling calculation along both the symmetric and the antisymmetric Ru-pyrazine-Ru stretching mode are presented. The results are in very good agreement with the reported experimental data and we are able to assign unambiguously this compound as a Class III system, following the Robin and Day classification. In this work we demonstrate that DFT does offer a unique tool for handling the localization−delocalization of electrons in mixed-valence systems and therefore we expect that this approach can play an important role in characterizing electron-transfer systems. Localized Ru−N(pyrazine) stretching in the range 254−275 cm-1 has been estimated from our calculations, which should be used in future model Hamiltonians...
Databáze:	OpenAIRE
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