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Dilute frozen solutions (1-2%) of specifically labelled n-hexane, n-heptane and n-octane in three halogenated matrices (CFCl 3 , CF 3 CCl 3  and CF 2 ClCFCl 2 ) have been X-irradiated at 77 K in order to produce the molecular cations. ESR spectra were recorded to temperatures up to the glass transition or melting points of the matrices. Several conformers differing in the geometric structure were observed. The 120° gauche conformers of the n-alkane molecular ions are stabilized by end D-labelling. Revised assignments of their coupling constants were obtained. The extended geometry was predominant in CFCl 3  with one exception. INDO MO calculations show that tilting of the CH 3  group towards the -CH 2 - chain lowers the energy and gives better agreement with experimental values for the hyperfine coupling constants. CF 3 CCl 3  seemed to induce the largest distortions in the geometry of the ions. The nature of a distorted conformer of hexane +  in CF 3 CCl 3  has been determined with the aid of observed couplings and INDO MO calculations.

ESR, Structure and Reactions of Specifically Deuterated C 6 — C 8 n-alkane Cations in Halogenated Matrices