An Exact Expression for Multidimensional Spectroscopy of a Spin‐Boson Hamiltonian

Abstract

Multidimensional coherent spectroscopy is a powerful tool to characterize nonlinear optical response functions. Typically, multidimensional spectra are interpreted via a perturbative framework that straightforwardly provides intuition into the density matrix dynamics that give rise to specific spectral features. When the goal is to characterize system coupling to a thermal bath however, the perturbative formalism becomes unwieldy and yields less intuition. Here, an approach developed by Vagov et al. is extended to provide an exact expression for multidimensional spectra of a spin‐boson Hamiltonian up to arbitrary order of electric field interaction. The utility of this expression is demonstrated by modeling polaron formation and coherent exciton‐phonon coupling in quantum dots, which strongly agree with experiment.