Multidimensional coherent spectroscopy of excitons in $π$-conjugated polymers

Abstract: The photophysics of $\pi$-conjugated polymers has been of considerable interest over the last three decades because of their organic semiconductor properties. Primary photoexcitations, Frenkel excitons, can be probed optically by means of numerous linear spectroscopies, providing a wealth of information on the the strength of excitonic coupling, the exciton coherence length, and on the nature of the disordered energy landscape. Nonetheless, there are intrinsic limitations in the information that can be obtained with linear spectroscopy compared to non-linear coherent techniques. Examples of this are the separation of homogeneous and inhomogeneous broadening contributions to the total exciton spectral lineshape, the detailed spectral structure of exciton-vibrational coupling, and correlations between optical excitations, including exciton-charge and exciton-exciton correlations. In the present work, we discuss the role of two-dimensional coherent excitation spectroscopy and review its applications towards unravelling the basic photophysics of $\pi$-conjugated polymers as well as polymer:fullerene blends, and we argue that these techniques are now valuable mainstream materials optical probes.