The structure of the l-propyl cation in the ion pair with the model anion trihydrofluoroborate, proven in earlier work to be appropriate for such studies, was investigated by ab initio calculations at the level previously reported to give the definitive structure of carbocations. In previous work, it was shown that the carbocation structure does not change with the nature of the anion, The cation structure is determined, however, by the distance between the cation and anion, d, and their relative orientation. At infinite interionic distance the only stable chemical species (energy minimum) is the protonated cyclopropane, 1. As the ions move toward each other, the cyclopropane bond opposite to the anion becomes progressively longer and eventually it breaks up in the contact ion pair. Three domains of cation stability are identified as a function of d: at long distances, ion 1 is the only energy minimum; at intermediate distances 1 and the l-propyl cation 2 are both energy minima; at short distances, ion 2 is the only energy minimum. Thus, ionization of l-propyl precursors forms the tight ion pair of 2 as the first intermediate. Isomers 1 and 2 differ in both the C1-C2-C3 angle and the conformation of the C2-C3 bond; the transition structure for their interconversion has been determined by calculations, At the MP4(FC)/6-311 G**//MP2/6-311G** level, the two isomers have the same energy content for d = 2.40 Angstrom, but correction for the zero-point energies obtained from the vibrational frequencies calculated at the MP2/6-311G** level reduces the energy of 2 relative to 1, thus requiring a slight upward correction in the value of d for equal stability of isomers. The interconversion of 1 and 2 is observed for a position of the anion essentially in the same plane as the three carbon atoms. Movement of the anion above the same plane results in hydrogen shift with the formation of the 2-propyl cation, 3, Some literature results in which primary carbocations could intervene as intermediates are discussed. In particular, the data on carbon and hydrogen scrambling in 3 in superacid solution are better accounted for by the results of calculations for ion pairs, with both 1 and 2 as intermediates, than by the results of calculations for isolated ions.