Current trends and future challenges in the experimental, theoretical and computational analysis of intervalence charge transfer (IVCT) transitions
D'Alessandro, Deanna M., and Keene, F. Richard (2006) Current trends and future challenges in the experimental, theoretical and computational analysis of intervalence charge transfer (IVCT) transitions. Chemical Society Reviews, 35 (5). pp. 424-440.
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Mixed-valence chemistry has a long and rich history which is characterised by a strong interplay of experimental, theoretical and computational studies. The intervalence charge transfer (IVCT) transitions generated in dinuclear mixed-valence species (particularly of ruthenium and osmium) have received considerable attention in this context, as they provide a powerful and sensitive probe of the factors which govern electronic delocalisation and the activation barrier to intramolecular electron transfer. This tutorial review discusses classical, semi-classical and quantum mechanical theoretical treatments which have been developed over the past 35 years for the analysis of IVCT absorption bands. Particular attention is drawn to the applicability of these models for the analysis of mixed-valence complexes which lie between the fully localised (Class II) and delocalised (Class III) limits in the ‘‘localised-to-delocalised’’ (Class II–III) regime. A clear understanding of the complex interplay of inter- and intramolecular factors which influence the IVCT process is crucial for the design of experimental studies to probe the localised-to-delocalised regime and in guidance of the development of appropriate theoretical models.
|Item Type:||Article (Refereed Research - C1)|
|Keywords:||mixed-valence, intervalence charge transfer, electron transfer theory|
Copyright 2006 Royal Society of Chemistry.
|Date Deposited:||10 May 2007|
|FoR Codes:||03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 100%|
|SEO Codes:||97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%|
|Citation Count from Web of Science||