Jl. Mchale, Subpicosecond solvent dynamics in charge-transfer transitions: Opportunities in Resonance Raman spectroscopy, ACC CHEM RE, 34(4), 2001, pp. 265-272
Resonance Raman spectroscopy is an established tool for the determination o
f structure and dynamics in electronically excited states. In condensed-pha
se systems, Raman excitation profiles and electronic absorption spectra dep
end on changes in molecular geometry and solvation structure induced by ele
ctronic excitation. Recent studies of solvent isotope effects on resonance
Raman intensities in charge-transfer excitations reveal solvent dynamics ta
king place on a subpicosecond time scale and vibrational mode-specific solu
te-solvent interactions. These discoveries present challenges to the curren
t working theories for analysis of resonance Raman and absorption spectra.