From the solvent dependence of the absorption band energies for metal-to-metal charge-transfer bands in several symmetrical ligand-bridged mixed-valence dimers, water emerges as an anomalous solvent. Explanations based on specific ligand-solvent interactions or the involvement of high-frequency hydroxyl stretching modes are shown to be inconsistent with the available results. The experimental observations can be accomodated, however, by postulating the involvement of relatively high-frequency librational modes known to exist in water. The observation of anomalously high MMCT band energies in water has significant implications for related electron-transfer reactions such as thermally activated self-exchanges.
|Original language||English (US)|
|Number of pages||3|
|Journal||Journal of Physical Chemistry|
|State||Published - Jan 1 1987|
ASJC Scopus subject areas
- Physical and Theoretical Chemistry