Towards a spectroscopic protocol for unambiguous detection of quantum coherence in excitonic energy transport

Abstract

The role of quantum effects in excitonic energy transport (EET) has been scrutinised intensely and with increasingly sophisticated experimental techniques. This increased complexity requires invoking correspondingly elaborate models to fit spectroscopic data before molecular parameters can be extracted. Possible quantum effects in EET can then be studied, but the conclusions are strongly contingent on the efficacy of the fitting and the accuracy of the model. To circumvent this challenge, we propose a witness for quantum coherence in EET that can be extracted directly from two-pulse pump–probe spectroscopy experimental data. We provide simulations to judge the feasibility of our approach. Somewhat counterintuitively, our protocol does not probe quantum coherence directly, but only indirectly through its implicit deletion. It allows for classical models with no quantum coherence to be decisively ruled out.