Yuen-Zhou, Joel, Jacob Krich, and Alan Aspuru-Guzik. 2012. “A witness for coherent electronic vs vibronic-only oscillations in ultrafast spectroscopy.” Journal of Chemical Physics 136 (23): 234501. doi:10.1063/1.4725498. http://dx.doi.org/10.1063/1.4725498.
We report a conceptually straightforward witness that distinguishes coherent electronic oscillations from their vibronic-only 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 in the singly excited manifold. 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.