Exciton-migration and three-pulse femtosecond optical spectroscopies of photosynthetic antenna complexes

A theory for four-wave-mixing signals from molecular aggregates, which includes effects of two-exciton states, static disorder, and coupling to a phonon bath with an arbitrary spectral density, is developed. The third-order polarization is rigorously partitioned into a coherent and a sequential contribution. The latter is given by a sum of an exciton-hopping and a ground state (bleaching) terms, both expressed using the doorway-window representation. Applications are made to photon-echo and pump-probe spectroscopies of the B850 system of the LH2 antenna in purple bacteria. (C) 1998 American Institute of Physics.