| Abstract
| - The absorption spectrum in the visible of [(NH3)5Ru(4,4‘-bipyridine)Ru(NH3)5]4+ in water has been studiedby extensive multireference configuration interaction calculations. Solvent effects were included by thepolarizable continuum model. Size and shape of the cavity surrounding the solute molecule were chosenaccording to a method that we have previously developed for systems in which solute−solvent hydrogenbonds occur. The dependence of the ground state, as well as that of the first singlet and triplet excited states,has been investigated as a function of the torsion between the two pyridine rings of 4,4‘-bipyridine. The lineshape profile of the metal-to-ligand charge transfer (MLCT) band has thus been obtained. The modificationsof the band due to a static electric field have then been studied, and the possible role of the triplet MLCTstate in determining the observed Stark spectrum has been investigated.
|
