Ultraviolet photoelectron spectra of 3-haloanilines

The He I and He II spectra of 3-haloanilines were measured and assigned usi ng a composite-molecule model. The assignments establish the relative order ing of the pi IEs (associated with the benzene moiety) and those associated with the nitrogen and in-plane halogen lone-pairs. These assignments are s ubstantiated by comparisons of He I and He IT cross-section ratios, ab init io calculations using the HF-6-31G** model, linear correlations of the in-p lane lone-pairs on the halogen substituent and Allred electronegativities f or the halobenzenes and haloanilines. Comparisons with the ultraviolet phot oelectron spectra of 2- and 4-haloanilines also reinforce these assignments . (C) 2000 Elsevier Science B.V. All rights reserved.