Spectroscopy from quantum dynamics: a mixed wave function/analytical line shape functions approach

Abstract Quantum dynamics is the natural framework in which accurate simulation of spectroscopy of nonadiabatically coupled molecular systems can be obtained. Even if efficient quantum dynamics approaches have been developed, the number of degrees of freedom that need to be considered in realistic systems is typically too high to explicitly account for all of them. Moreover, in open-quantum systems, a quasi-continuum of low-frequency environment modes need to be included to get a proper description of the spectral bands. Here, we describe an approach to account for a large number of modes, based on their partitioning into two sets: a set of dynamically relevant modes (so-called active modes) that are treated explicitly in quantum dynamics, and a set of modes that are only spectroscopically relevant (so-called spectator modes), treated via analytical line shape functions. Linear and nonlinear spectroscopy for a realistic model system is simulated, providing a clear framework and domain of applicability in which the introduced approach is exact, and assessing the error introduced when such a partitioning is only approximate.