Vibrational energy transfer processes

The CO laser resonance absorption technique is a useful tool for studying the dynamics of chemical reactions that involve the initial production of vibrationally excited CO molecules. We have recently applied this technique to study various atomic and free radical reactions related to combustion and electronic-to-vibrational energy transfer processes U—6). In this brief account, we discuss mainly the dynamics of 0(3P) + 1-alkynes and associated free radical reactions. 

Finally, it is interesting to note that Drummond [464] suggested a rather similar vibrational energy transfer process in order to explain why the apparent activation energy associated with the CO + Nj O induction periods was some 35 kcal. mole below the dissociation energy of N2O. 

Fig. 6. Nascent vibrational population distribution resulting from the electronic to vibrational energy transfer process I + I2(.X )...

COFj has found favour as a target molecule in energy transfer studies as its vibrational energy transfer processes are relatively little affected by rotational complications, its ir vibrational modes are all allowed and its constituent atoms are all of comparable large mass - a feature that means the vibrational modes are all easily accessible to one laser. 

C-H bonds in the solvent, as anticipated on the basis of Eqs. (20) and (21), was far better than with optical density parameters (Eq. (18)), and that such a situation was in accord with an electronic to vibrational energy transfer process of the exchange type. Thus, coupling between the highest frequency mode of the solvent and a vibronic transition of 02(1Ag) can be expressed... 

The fastest vibrational energy transfer processes are likely to be those involving near-resonant vibrational-vibrational (V-V) energy exchange. Thus for a diatomic molecule, processes such as... 

St. Lemont, G.W. Flynn, Vibrational state analysis of electronic-to-vibrational energy transfer processes. Annu. Rev. Phys. Chem. 28, 261 (1977)... 

---