Photoelectron spectra of inner valence shells. Part 1.—Saturated hydrocarbons

The 30.4 nm spectra of some saturated hydrocarbons are reported and it is shown that in most cases the energy spacing of the inner valence s type orbitals of these molecules can be accurately described in terms of simple Hückel expressions. The results of the analysis are used to comment on the “anomalous nature” of s type orbitals in the lower members of the cyclic paraffins. Vibrational analysis of the outermost s type bands of the methylmethanes is used as a basis for discussion of these orbitals and the nature of the C 2s orbital unit.