Two-Dimensional Electronic Stark Spectroscopy.

Characterizing ultrafast energy and charge transfer is important for understanding a wide range of systems, from natural photosynthetic complexes to organic photovoltaics. Distinguishing the kinetic processes of energy transfer and charge separation in such systems is challenging due to the lack of clear spectral signatures of charge transfer states, which are typically nonradiative. Stark spectroscopy has proven to be a valuable method for uncovering charge transfer states. Here we extend the dimensionality of Stark spectroscopy to perform two-dimensional electronic Stark spectroscopy. We demonstrate the method on TIPS-pentacene in 3-methylpentane at 77 K. The additional frequency dimension of two-dimensional Stark spectroscopy promises to enable the identification of charge transfer states, their coupling to other charge transfer and exciton states, and their involvement in charge separation processes.