We present a theoretical study of vibrationally resolved and unresolved molecular-frame photoelectron angular
distributions (MFPADs) resulting from K-shell photoionization of N2, CO, C2H2, NH3, CH4, CF4, BF3, and SF6
in the range of photoelectron energies 0–500 eV. We show that the MFPADs of NH3 and CH4, averaged over the
polarization direction, image the molecular geometry at very low energies but also at selected higher energies. For
all other molecules, the MFPADs do not image the system’s geometry. However, for molecules containing heavy
atoms in the periphery, CF4, BF3, and SF6, and for N2 and CO, the polarization-averaged MFPADs reflect the
partial accumulation of the photoelectron density in the region surrounded by the peripheral atoms. For energies
at which this accumulation occurs, the MFPADs encode information about the three dimensional arrangement
of the system. In general, the polarization averaged MFPADs remain quite anisotropic even at photoelectron
energies as high as 500 eV
