Photoelectron Spectra and Orbital Structures of Higher Alkyl Chlorides, Bromides, and Iodides

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High-resolution photoelectron spectra of alkyl halides RX (R=ethyl, n-propyl, and n-butyl; X=C1, Br, and I) were measured with the 584 Å line of helium. In the region below about 17 eV, six bands were observed for each of the ethyl halides, eight bands for each of the n-propyl halides, and ten bands for each of the n-butyl halides. All the observed vertical ionization energies were plotted against Pauling's electronegativity of the halogen atom, indicating that there are approximate linear relationships. Assuming Koopmans' theorem, total and partial sums of experimental orbital energies were calculated using the observed ionization energies for the individual alkyl halides and found to be well reproduced by calculating the sums of empirical orbital-energy values for several localized orbitals such as n(X.), n′(X), σ(C–X), σ(C–C), π(CH3), π′(CH3), and π(CH2). From a comparison of the experimental and calculated partial orbital-energy sums, assignments of the photoelectron bands to the localized molecular orbitals were made for each of the alkyl halides.
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