Abstract
The molecular excitontheory of sigma bonds, which was set up previously to explain the vacuum‐ultraviolet absorption spectra of alkanes, is applied here to the primary radiation chemical reactions of linear and branched alkane polymers. From this a number of theoretical predictions are made, the most important being that very efficient excitation energy transfer will occur along the CC bonds of the polymer main chains without causing main chain scission but that excitation energy in CH bonds will be localized in pairs of these bonds and give rise here to a high rate of scission. These predictions are examined in detail in the following two papers, using experimental data.