A study of the valence shell electronic structure of the 5-halouracils

Valence shell photoelectron spectra of the 5-halouracils have been recorded using synchrotron radiation at photon energies of 40 and 80 eV. Photoelectron angular distributions have been determined and these provide an experimental means of deducing the extent to which the molecular orbitals possess predominantly sigma, pi or halogen np character. In chloro-, bromo- and iodouracil two peaks, associated with the essentially halogen atom lone-pair orbitals, have been observed. The separation between these peaks, and the value of their photoelectron asymmetry parameters at an excitation energy of 40 eV, are compared with results for the corresponding orbitals in the halobenzenes and halothiophenes. Vertical ionisation energies and spectral intensities have been evaluated using the many-body Green's function approach, thereby enabling theoretical spectra to be derived. Assignments have been proposed for most of the structure observed in the valence shell photoelectron spectra based upon the available experimental and theoretical evidence. (C) 2008 Elsevier B.V. All rights reserved.