A witness for coherent electronic oscillations in ultrafast spectroscopy

Abstract

We report a conceptually straightforward witness that isolates coherent electronic oscillations from their vibronic counterparts in nonlinear optical spectra of molecular aggregates: Coherent oscillations as a function of waiting time in broadband pump/broadband probe spectra correspond to coherent electronic oscillations. Oscillations in individual peaks of 2D electronic spectra do not necessarily yield this conclusion. Our witness is simpler to implement than quantum process tomography and potentially resolves a long-standing controversy on the character of oscillations in ultrafast spectra of photosynthetic light harvesting systems.