Two dimensional electronic spectroscopy of molecular complexes

Two dimensional (2D) heterodyne-detected electronic photon echo spectroscopy is introduced and described. We give an intuitive description of the origin and information content of 2D electronic spectra, focusing on molecular complexes. We identify two important quantities-the transition dipole term, and the transition frequency cross correlation function that controls the appearance of 2D electronic spectra. We also show how the transition frequency cross correlation function controls the rate of exciton relaxation. These concepts are illustrated with experimental data on the seven bacteriochlorophyll FMO complex of a green sulfur bacterium, showing how the pathways and mechanisms of energy flow can be elucidated by combining 2D spectra with theoretical modeling.