Time-dependent laser-induced molecular

Time-dependent laser-induced molecular formation from repulsive surfaces [49, 52]... 

Th. Mercouris, l.D. Petsalakis, C.A. Nicolaides, Time-dependent laser-induced molecular formation from repulsive surfaces, Chem. Phys. Lett. 208 (1993) 197. 

Modem photochemistry (IR, UV or VIS) is induced by coherent or incoherent radiative excitation processes [4, 5, 6 and 7]. The first step within a photochemical process is of course a preparation step within our conceptual framework, in which time-dependent states are generated that possibly show IVR. In an ideal scenario, energy from a laser would be deposited in a spatially localized, large amplitude vibrational motion of the reacting molecular system, which would then possibly lead to the cleavage of selected chemical bonds. This is basically the central idea behind the concepts for a mode selective chemistry , introduced in the late 1970s [127], and has continuously received much attention [10, 117. 122. 128. 129. 130. 131. 132. 133. 134... 

The first volume contained nine state-of-the-art chapters on fundamental aspects, on formalism, and on a variety of applications. The various discussions employ both stationary and time-dependent frameworks, with Hermitian and non-Hermitian Hamiltonian constructions. A variety of formal and computational results address themes from quantum and statistical mechanics to the detailed analysis of time evolution of material or photon wave packets, from the difficult problem of combining advanced many-electron methods with properties of field-free and field-induced resonances to the dynamics of molecular processes and coherence effects in strong electromagnetic fields and strong laser pulses, from portrayals of novel phase space approaches of quantum reactive scattering to aspects of recent developments related to quantum information processing. 

Typically, in measurements of time-resolved luminescence in the time regime of tens of picoseconds, data obtained from 10 to 20 laser shots are averaged to improve the signal-to-noise ratio and to minimize the effects of shot-to-shot variations in the laser pulse energy and shape. Once the reliability of the data has been ensured by application of the corrections described above and made necessary by detector-induced distortions, the time-resolved fluorescence data is analyzed in terms of a kinetic model which assumes that the emitting state is formed with a risetime, xR, and a decay time, Tp. Deconvolution of the excitation pulse from the observed molecular fluorescence is performed numerically. The shape of the excitation pulse to be removed from the streak camera data is assumed to be the same as the prepulse shape, and therefore the prepulse is generally used for the deconvolution procedure. Figure 6 illustrates the quality of the fit of the time-dependent fluorescence data which can be achieved. 

Another aspect of optical pumping is related to the coherent excitation of two or more molecular levels. This means that the optical excitation produces definite phase relations between the wave functions of these levels. This leads to interference effects, which influence the spatial distribution and the time dependence of the laser-induced fluorescence. This subject of coherent spectroscopy is covered in Chap. 7. 

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