Geminate pair recombination

The yield (y) of the product of geminate pair recombination (ROCMe3) as a function of the subsequent rate constants [104,105] is given by... 

The discussion of Kapral s kinetic theory analysis of chemical reaction has been considered in some detail because it provides an alternative and intrinsically more satisfactory route by which to describe molecular scale reactions in solution than using phenomenological Brownian motion equations. Detailed though this analysis is, there are still many other factors which should be incorporated. Some of the more notable are to consider the case of a reversible reaction, geminate pair recombination [286], inter-reactant pair potential [454], soft forces between solvent molecules and with the reactants, and the effect of hydrodynamic repulsion [456b, 544]. Kapral and co-workers have considered some of the points and these are discussed very briefly below [37, 285, 286, 454, 538]. 

They have calculated the continuous diffusion equation (3.2.30) with U(r) = -a/r3 for several kinds of nn F, H centres in the crystalline lattice. Figure 3.9 demonstrates well that both defect initial separation and an elastic interaction are of primary importance for geminate pair recombination kinetics. The 3nn defects are only expected to have noticeable survival probability. Its magnitude agrees well with equation (3.2.60). 

The carbonyl component can be externally supplied as in the co-ozonolysis reactions (see Section 6.06.8.2) and other dipolarophiles can be used to trap the intermediate CO. Two types of rotations of the carbonyl component can take place relative to the CO <1997JOC2757> one type is in the plane of the heavy atoms which leads to the same stereochemistry as in the original alkene the other type is a rotation in a plane perpendicular to it leading to inversion. The preference of trans-alkenes to furnish in the gas phase the /raar-ozonides indicates a preference for the in-plane rotation and geminate pair recombination within the dipolar complex. At low temperatures this complex appears to be stabilized. 

The theoretical base of the spur process is Onsager s theory of the geminate pair recombination. Contrary to this, the blob model is most appropriate for consideration of early radiation-chemical processes in multiparticle track entities, such as blobs and ionization columns. The main distinction between the spur and blob comes from the large difference in the initial number of ion-electron pairs they contain. 

Schweitzer B, Arkhipov VI, Scheif U, Bassler H (1999) Geminate pair recombination in a conjugated polymer. Chem Phys Lett 313 57... 

Ries, B. and Bassler, H. Dynamics of geminate pair recombination in random organic solids smdied by Monte Carlo simulation, J. Mol. Electron., 3, 15, 1987. 

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