Charge transfer ionisation

Fig. 20 Variation of the fraction <5 of an electronic charge transferred from B to XY on formation of B- XY with the ionisation energy 7b of B for the series XY = 02, BrO and IO. See text for the method of determination of Si from observed XY nuclear quadrupole coupling constants. The solid curves are the functions <5 = A exp(- al ) that best fit the points for each series B- XY. Data for B- -B are nearly coincident with those of B- BrO and have been excluded for the sake of clarity...

Several of the primary ionisation processes listed in Table 4 yield H and Cl atoms as well as ions, and similar processes are observed with HBr and HI. Atoms may also be formed in secondary ion-molecule reactions which are discussed below. As shown in Table 5, the ionisation potentials of the halogen atoms and their hydrides are such that the charge transfer reaction... 

For reasons which will become apparent in section 1.8.2, it is assumed that each electron-ion pair eventually produces one molecule of hydrogen. In an earlier section (p. 160) it was seen that in HC1 an additional 0.20+0.2 hydrogen atoms per ion pair should come from dissociative ionisation and charge transfer processes. In the absence of hydrogen atom scavengers they will undergo the reaction... 

Fig. V.l. Frequency shift A = i>(35CI)a -v(3S Cl)AjcBy at 77 °K in charge transfer complexes as a function of the ionisation potential/. A = picrylchloride, C6H3(N02)3C1 x = y = 1. The number at the points measured note the substance B in the complex AB.

While TT-complexes play, as we shall see, a rather subsidiary role in the sequence of events leading to initiation in typical cationic systems, the formation of charge-transfer complexes can be directly responsible for the synthesis of active species. A charge-transfer complex, in Mulliken s meaning of the term, arises from the interaction of a donor mdecule having a low ionisation potential with an acceptor molecule... 

The charge transfer process of C5H22 with NO (ionisation potential 9.25 eV)... 

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