Two-dimensional photon-echo spectroscopy at a conical intersection: A two-mode pyrazine model with dissipation

The multi-dimensional electronic spectroscopy of ultrafast nuclear dynamics at conical intersections (CI) is an emerging field of investigation, which profits also from the recent extension of the techniques to the UV domain. We present a detailed computational study of oscillatory signatures in two-dimensional (2D) photon-echo spectroscopy (also known as 2D electronic spectroscopy, 2DES) for the two-mode pyrazine model with dissipation. Conventional 2D signals as well as the resulting beating maps are considered. Although of a reduced character, the model captures quite well all the main signatures of the excited-state dynamics of the molecule. Due to the ultrafast relaxation via the CI and no excited-state absorption from the low-lying dark state, the oscillatory components of the signal are found to be predominantly determined by the ground state bleach contribution. They reflect, therefore, the ground-state vibrational coherence induced in the Raman active mode. Beating maps provide a way to experimentally differentiate between ground state bleach and stimulated emission oscillatory components. The ultrafast decay of the latter constitutes a clear indirect signature of the CI. In the considered model, because of the sign properties of the involved transition dipole moments, the dominance of the ground-state coherence leads to anti-correlated oscillations of cross peaks located at symmetric positions with respect to the main diagonal.