Journal of Chemical Physics, Vol.113, No.18, 8113-8124, 2000
Chirped pulse excitation in condensed phases involving intramolecular modes studied by double-sided Feynman diagrams for fast optical dephasing
The effect of the quantum intramolecular modes on the chirped pulse excitation in condensed phase has been studied. Nonperturbative equations for the populations of molecular electronic states under the action of intense chirped pulses have been obtained using the double-sided Feynman diagrams. We have shown that the application of this technique to systems with fast electronic dephasing enables us to include strong system-bath interactions (non-Markovian relaxation) and to perform the summation of diagrams. We have studied the influence of the chirp rate on the integral population of the excited state n(2) after the completion of pulse action. We have shown that the effect of the quantum intramolecular modes strongly depends on the carrier pulse frequency. Incorporating these modes increases n(2) when a molecule is excited near the 0 -->1 transition with respect to the quantum intramolecular vibration. If the molecule is excited near the 0 -->0 transition with respect to the intramolecular mode, the effect is opposite.