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. (C) 1995 American Institute of Physics.