Abstract
Positive charge transfer between the initial cation and the solute has been reexamined in detail at 6 and 72 K for 3-methyloctane (3MO) glasses containing squalane (SQ). A good fit to the observed decay of the 3-methyloctane cation (3MO+) was obtained by using the tunneling expression. The binding energy calculated, B = 0.33 eV, does not agree with the electron tunneling model. The results are discussed in terms of alternate tunneling mechanisms. The positive charge transfer 3MO+ + SQ - 3M0 + SQ+ was separated kinetically from all other reactions, and the ratio t,,(SQ+)/cm,(3MO+) = 1.6 was calculated, in good agreement with an independent determination made by using pyrene (Py) as a cation scavenger. Positive charge transfer was also examined in several other mixed alkane systems.
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