Disentangling signal contributions in two-dimensional electronic spectroscopy in the pump–probe geometry

Since its introduction almost three decades ago, two-dimensional electronic spectroscopy (2DES) has evolved into a mature and powerful technique to reveal the inner workings of quantum systems with high temporal and spectral resolution. In general, this technique can isolate different contributions to the nonlinear response and provides access to different dynamical quantum pathways of the system evolution. Such isolation of pathways can be achieved in different experimental geometries. In its original, fully noncollinear implementation, directional phase matching allows for such signal isolation, while in the modern commonly employed pump-probe geometry, experimentally challenging phase-cycling schemes are employed. Here, we show how rephasing, non-rephasing, and zero- and double-quantum 2DES signals can be isolated in the pump-probe geometry without a need for phase-cycling. For this, we utilize established causality restrictions of the nonlinear response, allowing us to separate the different contributions in the spectral domain. We demonstrate this using data recorded for a molecular J-aggregate, acting as an effective three-level system. This approach bridges the gap between the capabilities of shaper-based and fully noncollinear 2DES and experimentally simpler implementations, such as those based on birefringent common-path interferometers.