A new formalism for the inner-sphere reorganization of ions involved in electron-trasnfer processes is presented. It is based on a simple model of reorganization phenomenon and utilizes the ion-dipole capture force field. The predictions of this model agree well with the experimental findings. For ions with weak ion-dipole force fields, such as halide ions, the statistical and perturbed rotational state models of ion-dipole capture are shown to give a satisfactory agreement with the experimental results. Correspondingly, for ion-dipole complexes involving strong force fields, such as multiple charged hexaaquo cations, the agreement between theory and experiment is obtained via the locked dipole orientation and the improved average dipole orientation models.
suggesting that a major factor in the mechanism of energy transfer involves fast exchange between resonant modes. It should be recalled that the IR spectra of SF6 and n-butane only overlap in the region at 950 ± 30 cm"1 corresponding to triply degenerate fundamental vibrations of both species. Notice that in highly excited n-C4H10+ energy losses would not longer be confined to individual modes due to fast intramolecular relaxation preceding decomposition.25 Inclusion of external rotations to the pool of sharing modes would not substantially modify the above arguments although they may contribute to relax resonance requirements. The fact that toluene is as efficient as SF6 despite having resonant modes at 730, 1500, and 2900 cm"1 reveals that the above conjecture awaits testing in similar experiments involving supersonic (25) M. L. Vestal, J. Chem. Phys., 43, 1356 (1965. beams of selected substrates. Further work is underway.Acknowledgment. Generous support from CIC of Argentina is gratefully acknowledged.
Appendix 1Let fx = "1 exp(-x/X) dx be the fraction of molecules which collide between x and (x + dx). Since in this case X(x) = V2'/Z(x), Z(x) = irbx2g«(x), and n(x) = n(0.6)(0.6/x)2, we get X(x) = ax2, with a = 20.1 (x in cm) and for the total fraction of molecules which have collided once after entering the beam before being detected at the ionizer: /= a"1 J exp(-l/ax)x"2 dx = 0.07
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