2D electronic-vibrational spectroscopy with classical trajectories.

Two-dimensional electronic-vibrational (2DEV) spectra have the capacity to probe electron-nuclear interactions in molecules by measuring correlations between initial electronic excitations and vibrational transitions at a later time. The trajectory-based semiclassical optimized mean trajectory approach is applied to compute 2DEV spectra for a system with excitonically coupled electronic excited states vibronically coupled to a chromophore vibration. The chromophore mode is in turn coupled to a bath, inducing redistribution of vibrational populations. The lineshapes and delay-time dynamics of the resulting spectra compare well with benchmark calculations, both at the level of the observable and with respect to contributions from distinct spectroscopic processes.