Nonlinear optical response of wave packets on quantized potential energy surfaces.

We calculated the dynamics of nuclear wave packets in coupled electron-vibration systems and their nonlinear optical responses. We found that the quantized nature of the vibrational modes is observed in pump-probe spectra particularly in weakly interacting electron-vibration systems such as cyanine dye molecules. Calculated results based on a harmonic potential model and molecular orbital calculations are compared with experimental results, and we also found that the material parameters regarding the geometrical structure of potential energy surfaces are directly determined by accurate measurement of time-resolved spectra.