The photoelectron spectra of some 1-halogenobicycloalkanes

Abstract
The HeI photoelectron spectra of the 1-bromo- and 1-iodo-substituted bicyclo[2.2.2]octane, bicyclo-[2.2.1]heptane, and bicyclo[2.1.1]hexane have been measured. Comparisons are made with the spectra of the corresponding alkanes, and assignments are derived with the assistance of HeII measurements and ab initio molecular orbital calculations based on a valence-electron model-potential method. The low-ionization-energy region of the spectra reveals interesting variations in the competition of spin–orbit coupling and conjugative effects which operate for ionizations involving the halogen lone-pair orbitals.

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