Correlated vibration-solvent and Duschinsky effects on electron transfer dynamics and optical spectroscopy

Abstract: Understanding the effects of vibrations in electron transfer (ET) dynamics and optical spectroscopies is essential to precisely interpret the role of decoherence, especially for systems embedded in solvents. In this work, we study the correlated Duschinsky and solvent effects on ET and spectroscopy. Exploited is a novel extended dissipaton-equation-of motion (ext-DEOM) approach, which is an exact and non-Markovian, non-perturbative method for quadratic system-bath couplings. The unified bath description, in terms of multiple Brownian oscillators (BOs), comprises the solvent modes and also intramolecular vibrations. Both ET dynamics and spectroscopy show the complex interplay among linear displacements, frequency shifts, Duschinsky rotations and solvent-induced BO-mode correlations. The reduced ET system density operator evolution is further analyzed in the context of Bloch sphere representation that is basis-set independent due to its geometric nature.