Two-dimensional spectroscopy beyond the perturbative limit: The influence of finite pulses and detection modes

Abstract

Ultra-fast and multi-dimensional spectroscopy gives a powerful looking glass into the dynamics of molecular systems. In particular, two-dimensional electronic spectroscopy (2DES) provides a probe of coherence and the flow of energy within quantum systems, which is not possible with more conventional techniques. While heterodyne-detected (HD) 2DES is increasingly common, more recently fluorescence-detected (FD) 2DES offers new opportunities, including single-molecule experiments. However, in both techniques, it can be difficult to unambiguously identify the pathways that dominate the signal. Therefore, the use of numerically modeling of 2DES is vitally important, which, in turn, requires appr..