Two-dimensional optical three-pulse photon echo spectroscopy. II. Signatures of coherent electronic motion and exciton population transfer in dimer two-dimensional spectra.

Using the nonperturbative approach to the calculation of nonlinear optical spectra developed in a foregoing paper [Mancal et al., J. Chem. Phys. 124, 234504 (2006), preceding paper], calculations of two-dimensional electronic spectra of an excitonically coupled dimer model system are presented. The dissipative exciton transfer dynamics is treated within the Redfield theory and energetic disorder within the molecular ensemble is taken into account. The manner in which the two-dimensional spectra reveal electronic couplings in the aggregate system and the evolution of the spectra in time is studied in detail. Changes in the intensity and shape of the peaks in the two-dimensional relaxation spectra are related to the coherent and dissipative dynamics of the system. It is shown that coherent electronic motion, an electronic analog of a vibrational wave packet, can manifest itself in two-dimensional optical spectra of molecular aggregate systems as a periodic modulation of both the diagonal and off-diagonal peaks.