The theory of photon echoes for strongly coupled electron–phonon systems
James L. Skinner
We calculate the photon echo decay for a strongly coupled electron–phonon system, without making unrealistic assumptions about excitation pulse durations. We find that asymptotically, the photon echo decay is exponential, and we provide a formal expression for the decay rate 1/T2 which is independent of pulse duration. In contrast to the usual results, our expression for 1/T2 is nonperturbative in the electron–phonon interaction. We calculate the dependences of the echo amplitude on pulse power and duration, finding that the strong electron–phonon coupling modifies the simple two level system result. We also focus on the relationship between the zero phonon line shape in the homogeneous optical absorption spectrum, and the photon echo decay rate. We find that the zero phonon line shape is Lorentzian, with width 1/πT2. We show that the usual optical Bloch equation approach to analyzing time-domain experiments, which normally is only applicable if the electron–phonon coupling is weak, can be extended to the case of strong coupling. These strong coupling Bloch equations are adequate for analyzing the time dependence, but not the pulse power and duration dependences, of time-domain experiments. Our results indicate that within the Condon approximation, electron–phonon coupling cannot explain the very low temperature anomaly of recent photon echo experiments on impurities in molecular crystals.
The Journal of Chemical Physics•Oct 1, 1982•29 citations