Spectroscopic coherent transients

A number of laser based temporal domain experiments have evolved in the past two decades which have no equivalents in conventional spectroscopic technique as they exploit the coherence inherent to stimulated sources. The origin of these methods traces directly to techniques which are widely utilized in NMR and ESR spectroscopy to determine various relaxation and dephasing times. In fact, much of the terminology from magnetic resonance processes has been carried over to laser driven coherent transient studies. See Shoemaker (1978), Levenson (1982) and Brewer and DeVoe (1984). 

Introduction. - Fundamental Physical Applications of Laser Spectroscopy. - Two and Three Level Atoms/High Resolution Spectroscopy. - Rydbeig States. - Multiphoton Dissociation, Multiphoton Excitation. - Nonlinear Processes, Laser Induced Collisions, Multiphoton Ionization. - Coherent Transients, Time Domain Spectroscopy, Optical Bistability, Superradiance. - Laser Spectroscopic Applications. - Laser Sources. - Postdeadline Papers. - Index of Contributors. 

The next two chapters are devoted to ultrafast radiationless transitions. In Chapter 5, the generalized linear response theory is used to treat the non-equilibrium dynamics of molecular systems. This method, based on the density matrix method, can also be used to calculate the transient spectroscopic signals that are often monitored experimentally. As an application of the method, the authors present the study of the interfadal photo-induced electron transfer in dye-sensitized solar cell as observed by transient absorption spectroscopy. Chapter 6 uses the density matrix method to discuss important processes that occur in the bacterial photosynthetic reaction center, which has congested electronic structure within 200-1500cm 1 and weak interactions between these electronic states. Therefore, this biological system is an ideal system to examine theoretical models (memory effect, coherence effect, vibrational relaxation, etc.) and techniques (generalized linear response theory, Forster-Dexter theory, Marcus theory, internal conversion theory, etc.) for treating ultrafast radiationless transition phenomena. 

By using transient absorption spectroscopic techniques, time-resolved measurements of photo-induced interfacial ET with time-constants shorter than 100 fsec have become possible [51,52,58-60]. When ultrashort laser pulses are used in studying PIET, vibrational coherences (or vibrational wave packet) can often be observed and have indeed been observed in a number of dye-sensitized solar cell systems. This type of quantum beat has also been observed in ultrafast PIET in photosynthetic reaction center [22], It should be noted that when the PIET takes place in the time scale shorter than 100 fsec, vibrational relaxation between the system and the heat bath is slower than PIET this is the so-called vibrationally non-relaxed ET case, and it will be treated in this section. 

Figure 5 presents the frequency ranges that, by optimistic estimates, can be covered by the optical techniques discussed above. We have intentionally left out of the discussion several other optical spectroscopic methods, such as coherent anti-Stokes resonant scattering (CARS), or induced transient grating (TG) spectroscopy, mainly because they are rarely used in the present context and/or are much less straightforward to interpret. 

Besides various detection mechanisms (e.g. stimulated emission or ionization), there exist moreover numerous possible detection schemes. For example, we may either directly detect the emitted polarization (oc PP, so-called homodyne detection), thus measuring the decay of the electronic coherence via the photon-echo effect, or we may employ a heterodyne detection scheme (oc EP ), thus monitoring the time evolution of the electronic populations In the ground and excited electronic states via resonance Raman and stimulated emission processes. Furthermore, one may use polarization-sensitive detection techniques (transient birefringence and dichroism spectroscopy ), employ frequency-integrated (see, e.g. Ref. 53) or dispersed (see, e.g. Ref. 54) detection of the emission, and use laser fields with definite phase relation. On top of that, there are modern coherent multi-pulse techniques, which combine several of the above mentioned options. For example, phase-locked heterodyne-detected four-pulse photon-echo experiments make it possible to monitor all three time evolutions inherent to the third-order polarization, namely, the electronic coherence decay induced by the pump field, the djmamics of the system occurring after the preparation by the pump, and the electronic coherence decay induced by the probe field. For a theoretical survey of the various spectroscopic detection schemes, see Ref. 10. 

Note that the application of the convolution scheme in the simple form (44) requires that the nonlinear polarization contains only a single interaction with the probe laser field. Apart from the transient transmittance spectrum considered above, this condition is also fulfilled for related detection schemes such as time-resolved fluorescence, ionization, and excited-state absorption. Coherent spectroscopic signals such as the photon-echo, on the other hand, contain two interactions with the probe laser field, thus requiring the calculation of the full three-time response function, followed by a double convolution. 

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