Journal of Chemical Physics, Vol.103, No.19, 8346-8359, 1995
The Solvent Spectral Density and Vibrational Multimode Approach to Optical Dephasing - 2-Pulse Photon-Echo Response
A rigorous theoretical connection between the polarizability spectral density obtained from optical Kerr effect (OKE) measurement with the correlation function describing solvent-induced optical dephasing detected in photon echo measurements is given. The experimentally obtained spectral density has a more reasonable physical basis than model correlation-function descriptions of solvent fluctuations. The experimental OKE spectrum is demonstrated to provide a natural description of solvent motions that modulate the chromophore electronic states in the case of weak induced-dipolar interactions. The chromophore optically active vibrational modes are obtained from pump-probe spectra and are employed in the calculation of echo signals. It is found that the fast decays of the two-pulse echo signals result from both solvent and solute intramolecular motions while the echo peak shifts are dominated by the solvent intermolecular modes.
Keywords:SUB-DOPPLER SPECTROSCOPY;PUMP-PROBE EXPERIMENTS;LARGE MOLECULES;RAMAN-SCATTERING;QUANTUM BEATS;FEMTOSECOND;ABSORPTION;DYNAMICS;LIQUIDS;SYSTEM