Time-resolved spectroscopies photon echo

In this paper we report the use of spectrally resolved two-colour three-pulse photon echoes to expand the information that can be obtained from time-resolved vibrational spectroscopy. The experiments allow the study of intramolecular dynamics and vibrational structure in both the ground and excited electronic states and demonstrate the potential of the technique for studying structural dynamics. 

When deciding to study the dynamics of electronic excitation energy transfer in molecular systems by conventional spectroscopic techniques (in contrast to those based on non-linear properties such as photon echo spectroscopy) one has the choice between time-resolved fluorescence and transient absorption. This choice is not inconsequential because the two techniques do not necessarily monitor the same populations. Fluorescence is a very sensitive technique, in the sense that single photons can be detected. In contrast to transient absorption, it monitors solely excited state populations this is the reason for our choice. But, when dealing with DNA components whose quantum yield is as low as 10-4, [3,30] such experiments are far from trivial. 

While the first experiments of time-resolved IR spectroscopy were conducted with pulse durations exceeding 10 ps, the improved performance of laser systems now offers subpicosecond (12) to femtosecond (13-15) pulses in the infrared spectral region. In addition, the pump-probe techniques have been supplemented by applications of higher-order methods, e.g., IR photon echo observations (16). 

Relaxations of solvent-chromophore interactions can be studied experimentally by hole-burning spectroscopy, time-resolved pump-probe measurements, and photon-echo techniques that we discuss in the next chapter. If the temperature is low enough to freeze out pure dephasing, and a spectrally narrow laser is used to bum a hole in the absorption spectmm (Sect. 4.11), the zero-phonon hole should have the Lorentzian lineshape determined by the homogeneous lifetime of the excited state. The hole width increases with increasing temperature as the pure dephasing associated with tP comes into play [36, 37]. 

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