Near-infrared active molecules

Very large rate constants have been found for near resonant energy transfer between infrared active vibrations in CO2 Such near-resonant transitions and their dependence on temperature have also been studied for collisions between vibrationally excited CO2 and other polyatomic molecules as CH4, C2H4, SF et al. The deactivation cross-sections range from 0.28 for CH3F to 4.3 for SFs at room temperature, and decrease with increasing temperature. 

The complex quantity, y6br = e (y(3)r) + i Im (x r), represents the nuclear response of the molecules. The induced polarization is resonantly enhanced when the Raman shift wp — ws matches the frequency Qr of a Raman-active molecular vibration (Fig. 6.1A). Therefore, y(3)r provides the intrinsic vibrational contrast mechanism in CRS-based microscopies. The nonresonant term y6bnr represents the electronic response of both the one-photon and the two-photon electronic transitions [30]. Typically, near-infrared laser pulses are used to prevent the effect of two-photon electronic resonances. With input laser pulse frequencies away from electronic resonances, y(3)nr is independent of frequency and is a real quantity. It is important to realize that the nonresonant contribution to the total nonlinear polarization is simply a source for an unspecific background signal, which provides no chemical contrast in some of the CRS microscopies. While CARS detection can be significantly effected by the nonresonant contribution y6bnr [30], SRS detection is inherently insensitive to it [27, 29]. As will be discussed in detail in Sects. 6.3 and 6.4, this has major consequences for the image contrast mechanism of CARS and SRS microscopy, respectively. 

Near-infrared absorption is therefore essentially due to combination and overtone modes of higher energy fundamentals, such as C-H, N-H, and O-H stretches, which appear as lower overtones and lower order combination modes. Since the NIR absorption of polyatomic molecules thus mainly reflects vibrational contributions from very few functional groups, NIR spectroscopy is less suitable for detailed qualitative analysis than IR, which shows all (active) fundamentals and the overtones and combination modes of low-energy vibrations. On the other hand, since the vibrational intensities of near-infrared bands are considerably lower than those of corresponding infrared bands, optical layers of reasonable size (millimeters, centimeters) may be transmitted in the NIR, even in the case of liquid samples, compared to the layers of pm size which are detected in the infrared. This has important consequences for the direct quantitative study of chemical reactions, chemical equilibria, and phase equilibria via NIR spectroscopy. 

Several of the polymethine dyes absorb in the red, far-red, and near-infrared and fluoresce efficienlly as well in this spectroscopic region. Functional derivatives of these may provide excellent fluorescent labels for semiconductor laser excitation. Several research groups are currently actively involved in the synthesis and development of large polyunsaturated dye molecules that are excited and show luminescence in the red and near-infrared. This promises to be one of the most exciting areas of luminescence spectroscopy for the foreseeable future. 

Syntheses of additional analogues with a different number of fused rings are in progress. A systematic evaluation of the activities of these molecules in biological systems will provide a sound basis for the application of red and near-infrared laser... 

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