Spectral lineshapes in nonlinear electronic spectroscopy

摘要: We outline a computational approach for nonlinear electronic spectra, which accounts the energy fluctuations due to nuclear degrees of freedom and explicitly incorporates higher excited states, induced by dynamics in photoactive state(s). This is based on mixed quantum-classical simulations. Tedious averaging over multiple trajectories avoided employing linearly displaced Brownian harmonic oscillator model correlation functions. The present strategy couples accurate computations high-lying state manifold with application made two-dimensional spectra pyrene, polycyclic aromatic hydrocarbon characterized an ultrafast (few tens femtoseconds) decay from bright S2 dark S1 state. waiting times t2 = 0 1 ps demonstrate ability this realistic lineshapes. Comparison experimental [Krebs et al., New Journal Physics, 2013, 15, 085016] shows excellent agreement allows us unambiguously assign absorption features.