Franck-Condon proton

Due to strong interaction of the reactants with the medium, the influence of the latter may not be reduced only to the widening of the vibrational levels of the proton in the molecules AH and BH. The theory takes into account the Franck-Condon factor determined by the reorganization of the medium during the course of the reaction. 

In an outer-sphere electron transfer the actual electron transfer is iso-energetic and takes place in 10 16 s, during which time, by the Franck-Condon principle, the heavier nuclei do not move. Since protons are known to tunnel (Bell et ah, 1956 Bell, 1973 Caldin, 1969 Lewis, 1975) and since the electron is 2000 times lighter than the proton, it is almost certain that in the actual electron transfer the electron tunnels. For instance, in an isotopic mixing experiment (16) the barrier to the reaction (k = 8 m-1 s-1) lies in achieving the... 

The protonated cluster ions were observed to be the major product ions in the CMS of ammopia, water, etc., although unprotonated cluster ions have also been observed in these cases, depending on the choice of carrier gas, method of ionization, and electron energy utilized in the investigation (Shinohara et al. 1985, 1986). The inability to observe unprotonated cluster ions is usually attributed to poor Franck-Condon factors for the vertical ionization transitions. These poor Franck-Condon factors arise from the large differences in the configuration of the neutral and ionic clusters (Stace 1987a). 

Combining equation (17) with expressions for the standard reduction of A + (env) and for the formation and hydration of the proton, we obtain the Franck Condon parameters as follows ... 

In the second chapter, Appleby presents a detailed discussion and review in modem terms of a central aspect of electrochemistry Electron Transfer Reactions With and Without Ion Transfer. Electron transfer is the most fundamental aspect of most processes at electrode interfaces and is also involved intimately with the homogeneous chemistry of redox reactions in solutions. The subject has experienced controversial discussions of the role of solvational interactions in the processes of electron transfer at electrodes and in solution, especially in relation to the role of Inner-sphere versus Outer-sphere activation effects in the act of electron transfer. The author distils out the essential features of electron transfer processes in a tour de force treatment of all aspects of this important field in terms of models of the solvent (continuum and molecular), and of the activation process in the kinetics of electron transfer reactions, especially with respect to the applicability of the Franck-Condon principle to the time-scales of electron transfer and solvational excitation. Sections specially devoted to hydration of the proton and its heterogeneous transfer, coupled with... 

It is important that, according to Fig. 25, the information concerning the correspondence of high frequency vibrations of the deuterated ligand relative to those of the protonated figand is available. A similar correlation has also been carried out for those vibrational modes that are Franck-Condon active with respect to the emission from state II, for details see Ref. [23]. 

The new ingredients are Franck-Condon factors of the initial (final) state proton vibronic wavefunctions(Zfn)- e initial states are summed over the... 

---