Intramolecular Charge Transfer of Curcumin and Solvation Dynamics of DMSO Probed by Time-Resolved Raman Spectroscopy.

Intramolecular charge transfer (ICT) of curcumin in dimethyl sulfoxide (DMSO) solution in the excited state was investigated by femtosecond electronic and vibrational spectroscopy. Excited-state Raman spectra of curcumin in the locally-excited and charge-transferred (CT) state of the S 1 excited state were separated due to high temporal (<50 fs) and spectral (<10 cm -1 ) resolutions of femtosecond stimulated Raman spectroscopy. The ultrafast (0.6-0.8 ps) ICT and subsequent vibrational relaxation (6-9 ps) in the CT state were ubiquitously observed in the ground- and excited-state vibrational modes of the solute curcumin and the ν CSC and ν S=O modes of solvent DMSO. The ICT of curcumin in the excited state was preceded by the disruption of the solvation shells, including the breakage of hydrogen bonding between curcumin and DMSO molecules, which occurs at the ultrafast (20-50 fs) time scales.