Role of Mode-mode Coupling in Short-time Excited State Decay

Master equation of a relevant electronic and vibrational system is derived for a special diabatic basis corresponding to vertical processes. It is shown that bath modes contribute dynamically to the inter-state coupling only at short times. For long times the bath-induced inter-state coupling is static and increases with the contribution of bath modes to the Stokes shift and to the Herzberg-Teller correction of the excited state. Simultaneously, the time evolution of excited state population is studied numerically for the system consisting of two electronic levels interacting with two vibrational modes, coupled to a heat bath. A mutual coupling of the vibrational modes in the excited state is taken into account (Duschinsky effect). Excited state population relaxes faster if interacting vibrational mode dissipates its energy via vibrational mode of a smaller eigenfrequency. Fast component of excited state depopulation cannot be achieved via coherent mode-mode coupling, if the second mode is not directly coupled to the electronic inter-state transition.