Results of an experimental study of the valence electronic structure of difuoromethane employing high-resolution Electron Momentum Spectroscopy with various impact energies are reported. One-particle Green's Function theory is utilized, for the first time, for computing accurate spherically averaged electron momentum distributions. These are derived from Dyson orbitals obtained using the third-order Algebraic Diagrammatic Construction (ADC(3)) scheme. The corresponding eigen-energies also accurately reproduce the (e,2e) ionization spectrum. Shortcomings of empirical analyses of (e,2e) experiments based on Kohn-Sham orbitals and eigen-energies are comparatively discussed. A failure of the target Hartree-Fock approximation is noted for the momentum distribution pertaining to the 1b(1) + 3b(2) + 5a(1) levels. (c) 2006 Elsevier B.V. All rights reserved.