Coherent and dissipative quantum process tensor reconstructions in two-dimensional electronic spectroscopy.

A major goal of time-resolved spectroscopy is to resolve the dynamical processes that follow photoexcitation. This amounts to identifying all the quantum states involved and the rates of population transfer between them. Unfortunately, such quantum state and kinetic reconstructions are ambiguous using one-dimensional methods such as transient absorption even when all the states of the system are fully resolved. Higher-dimensionality methods like two-dimensional spectroscopy lift some of the ambiguity, but unless the spectral features are well-separated, current inversion methods generally fail. Here, we show that, using both coherence and population signals of the nonlinear response, it is indeed possible to accurately extract both static and dynamic information from the 2D spectrum even when features are highly congested. Coherences report on the positions of the vibronic states of the system, providing a useful constraint for extracting the full kinetic scheme. We model time-resolved 2D photon echo spectra using a sum-over-states approach and show in which regimes the Hamiltonian and kinetic schemes may be recovered. Furthermore, we discuss how such algorithms may be applied to experimental data and where some of the underlying assumptions may fail. The ability to systematically extract the maximal information content of multidimensional spectroscopic data is an important step toward utilizing the full power of these techniques and elucidating the structure and dynamics of increasingly complex molecular systems.