To calibrate computational studies of photoelectron spectra of dissolved anions, the vertical electron detachment energies (VEDEs) of the fluoride and chloride anions in isolation and in the presence of six coordinated water molecules have been calculated with and without the polarizable continuum model (PCM) of solvation in water. Large shifts in VEDEs and important changes in coordination geometries about the chloride anion occur with the use of the PCM. Cluster and PCM calculations confirm previous, qualitative conclusions on Dyson orbitals corresponding to the lowest VEDEs of aqueous halide anions. For the fluoride case, Dyson orbitals for the lowest VEDEs are spread over water molecules, not the anion, but for the chloride case, the Dyson orbitals for the lowest VEDEs are localized on the anion. The partial third-order (P3) and P3+ approximations of electron propagator theory provide a reliable means to calculating VEDEs with polarized atomic basis sets. © 2012 Wiley Periodicals, Inc.