Vibrational response functions for multidimensional electronic spectroscopy in nonadiabatic models

The interplay of nuclear and electronic dynamics characterizes the multidimensional electronic spectra of various molecular and solid-state systems. Theoretically, the observable effect of such interplay can be accounted for by response functions. Here, we report analytical expressions for the response functions corresponding to a class of model systems. These are characterized by coupling between the diabatic electronic states and the vibrational degrees of freedom, resulting in linear displacements of the corresponding harmonic oscillators, and by nonadiabatic couplings between pairs of diabatic states. In order to derive the linear response functions, we first perform the Dyson expansion of the relevant propagators with respect to the nonadiabatic component of the Hamiltonian, then derive and expand with respect to the displacements the propagators at given interaction times, and finally provide analytical expressions for the time integrals that lead to the different contributions to the linear response function. The approach is then applied to the derivation of third-order response functions describing different physical processes: ground state bleaching, stimulated emission, excited state absorption, and double quantum coherence. Comparisons between the results obtained up to sixth order in the Dyson expansion and independent numerical calculation of the response functions provide evidence of the series convergence in a few representative cases.

Automated summary

The observable effect of the interplay between nuclear and electronic dynamics on multidimensional electronic spectra can be accounted for by response functions. In this study, we derive analytical expressions for the response functions corresponding to a specific class of model systems, which are characterized by coupling between electronic states and vibrational degrees of freedom, as well as nonadiabatic couplings between pairs of diabatic states. The approach is applied to derive third-order response functions for various physical processes and comparisons with numerical calculations provide evidence of convergence in selected cases.