Resonance Raman analysis of charge-transfer reorganization energies in a covalent dicyanoethylene-aza-adamantane

Resonance Raman cross sections have been measured for a covalent electron donor-acceptor substituted aza-adamantane. Excitation near the maximum of the strong charge-transfer absorption results in resonance enhancement of a number of Raman fundamentals, overtones, and combination bands. The reorganization energy in each molecular mode and the solvent contribution to the electronic linewidth are determined through quantitative modeling of the absorption, Raman, and fluorescence spectra, which are sensitive to solvent dynamics on different time scales. The results suggest that the solvent-induced broadening in methanol has components that fluctuate on a wide range of timescales.