High frequency intramolecular modes

High-frequency intramolecular modes and shifts are represented by a single effective frequency. 

Figure 2.4. The energy-gap dependence of the nuclear Franck-Condon factor, which incorporates the role of the high-frequency intramolecular modes. Sc = A/2 is the dimensionless electron-vibration coupling, given in terms which reduce replacement (A) between the minimum of the nuclear potential surfaces of the initial and final electronic states. (Bixon and Jortner, 1999) Reproduced with permission.

To conclude, it seems that the nature of the anharmonic coupling between a high frequency intramolecular mode and a thermally excited low frequency mode is understood. It turns out that the strength of the influence on the infrared spectrum critically depends on the values of (Oq, Sm and t. However, we have to wait for more experimental data on these low frequency modes, probably obtained with the helium atom scattering technique, bdbre we can make more definite conclusions. 

While being very similar in the general description, the RLT and electron-transfer processes differ in the vibration types they involve. In the first case, those are the high-frequency intramolecular modes, while in the second case the major role is played by the continuous spectrum of polarization phonons in condensed 3D media [Dogonadze and Kuznetsov 1975]. The localization effects mentioned in the previous section, connected with the low-frequency part of the phonon spectrum, still do not show up in electron-transfer reactions because of the asymmetry of the potential. 

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