Where’s the Spin? A DFT Study of Mixed-Valence Cyanide-Bridged Ruthenium Polypyridines

This article discusses the use of density functional theory (DFT) calculations in classifying and characterizing bimetallic ruthenium mixed-valence systems in terms of their electronic localization/delocalization degree. A standard B3LYP/LanL2DZ methodology including integral equation formalism-polarizable continuum model (IEF-PCM) solvent model is evaluated for a set of 16 non-symmetric mixed-valence cyanide-bridged ruthenium polypyridines. This procedure reproduces well the features of the observed electronic and vibrational spectra, with better agreement for the more delocalized systems, an...