Download Ultrafast Infrared And Raman Spectroscopy (Practical by M.D. Fayer PDF
By M.D. Fayer
An outline of tactics for probing bond activation, H-bonded structures, molecular dynamical mechanisms, vibrational dephasing, easy beverages, and proteins and effort stream results utilizing ultrafast vibrational spectroscopy experiments. It discusses experimental and theoretical equipment of ultrafast infrared and Raman measurements.
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Extra resources for Ultrafast Infrared And Raman Spectroscopy (Practical Spectroscopy)
Example text
The population lifetime T1 of the mode Copyright © 2001 by Taylor & Francis Group, LLC displays little dependence on the number of CH groups of the alcohol and on the apolar solvents leading to numbers of 8–10 ps. The data suggest that intramolecular energy redistribution is dominant; in fact, the solvent molecules do not not offer suitable accepting modes for vibrational energy transfer of the OH vibration. The relaxation pathway was studied in detail in the case of monomeric ethanol (73). From time-delayed bleaching at CHstretching frequencies intramolecular relaxation via these vibrations was inferred.
5c after proper deconvolution of the nonresonant contribution (data not shown). Corresponding lineshape data of the isotropic component of spontaneous Raman scattering are presented in Fig. 8b. Knowing T2 within š30 fs (Fig. 5), the measured lineshape (experimental points) is readily plotted versus normalized frequency units ω ð T2 . Comparison with the computed lineshapes [Fourier transformation of Equation (9)] leads to 350 š 100 fs for c , in good agreement with the time-domain results. Combining the measurements, one arrives at c D 330 š 70 fs (45).
The polarization dependence of the probe transmission is computed by integration over the orientational distributions, while the reorientational motion is treated in the limit of rotational diffusion (64). In a more general approach coherent effects can be also included; the finite T2 plays an important role for the time evolution of spectral holes (63). As a simple example a three-level system with slow reorientation is considered. States (0) and (1) are directly coupled to the excitation pulse, while the intermediate level (2) is populated in the relaxation path of the excess population N1 of the upper level on its way back to the ground state.