Time Evolution of Vibration-Induced Excited State Decay

A simple model consisting of two electronic levels and one vibrational mode (phonon) was theoretically studied. The electronic-vibrational interaction was linear in the vibrational displacement. The vibrational mode was taken in the harmonic approximation and was attached to the thermal bath formed by the ambient environment. The kinetic constants of the vibrational dissipation were of the second order in the vibrational-bath coupling and were taken in the Markovian limit. Although, depending on the parameters of the model, different curves of the non-radiative vibration-induced excited state decay were obtained, in general, three time intervals, corresponding to different physical behaviour, were found. In the short-time interval, small oscillations superimposed on the excited state decay were observed. They were determined by the vibrational frequency and influenced by electronic-vibrational coupling. In the middle-time interval, almost quasi-exponential decay was detected; its rate constant increased with stronger electronic-vibrational interaction and speed of vibrational relaxation. In the long-time interval, the decay was very slow and, under special conditions, even an asymptotic non-zero excited state population was observed. Its value increased with the strength of the off-diagonal electron-vibrational coupling. Links of the parameters of the model with quantum chemical terms were estimated.