Antibonding orbitals belong to the valence space, and contribute to making a minimal basis that can be used to gain insight into chemistry, for instance via population analysis to assign effective charges on each atom. The population analysis we present here is constructed from the union of the occupied space and the antibonding orbitals without dependence on the basis set used. To study our atomic charge predictions and compare it to some other methods in the literature, we look into fluoro-and chloro-substituted methanes which have been studied theoretically 101-103 and experimentally. 104,105 These simple systems are nonetheless interesting because they manifest the effect of substituting electron withdrawing halogen atoms of different sizes and electronegativities for hydrogen in methane. How consistent or inconsistent are different atomic population analysis schemes as descriptors of these chemical substitutions?