Influence of neighboring levels in three-pulse photon-echo processes

Abstract

It is the purpose of the present paper to study the dynamics underlying a three-pulse photon-echo process performed on a vibronic system coupled to non-Markovian baths, when a neighboring level enters into the global dynamical evolution because of broadband excitation required in these experiments. Particular emphasis is on the energy gap between the vibronic levels, but also on the fluctuation amplitudes and correlation times of their corresponding thermal baths. The photon-echo signal appears to be very sensitive to the additional interfering contributions introduced by the neighboring vibronic level. It is shown that these contributions associated to the pathways involving different vibronic states are modulated by their corresponding energy gap. As a consequence, these contributions to the integrated photon-echo signal strongly decrease for large energy gaps. Also, an oscillating behavior is observed on the time dependence of the photon-echo signal resulting from the summation of the contributions provided by the individual vibronic levels. Moreover, the influence of the non-Markovian character of the baths, accountable for inhomogeneous broadening, affects the amplitude and the time dependence of the photon-echo signal, as well as its dependence with the delay time of the laser pulses. Of course, for longer times a Markovian dynamical evolution is recovered.