INTRAMOLECULAR ELECTRON-TRANSFER IN BIFERROCENE MONOCATION - EVALUATION OF FRANCK-CONDON EFFECTS VIA A TIME-DEPENDENT ANALYSIS OF RESONANCERAMAN-SCATTERING IN THE EXTENDED NEAR-INFRARED

Franck-Condon effects associated with intramolecular electron transfer in the biferrocene monocation have been evaluated via time-dependent analyses of resonance Raman scattering intensities and the intervalenc e absorption line shape. Quantitative studies in the extended near-inf rared (1320 and 1064 nm excitation) reveal that-three vibrational mode s are displaced in the electron-transfer process. The most significant of these, the symmetrical ring-Fe-ring stretch, has also been implica ted in prior X-ray crystallographic studies. Mode or bond displacement s obtained from the Raman analysis are slightly larger than estimates based on crystallographic displacements. These differences together wi th contributions from two additional modes identified by Raman appear to account for seemingly disparate estimates of vibrational reorganiza tion energies provided by (a) the crystallographic method and (b) ''Pe kar plot'' intercepts derived from intervalence absorption maxima. Imp lications for electron exchange kinetics are also discussed.