In this work we examined four different electronic structure method/basis set combinations to determine which might provide a reasonable and accurate foundation for the derivation of fixedcharge electrostatic models to be used in molecular mechanics force fields. To do this we looked at both the strength and consistency of each combination's overpolarization. We found that the HF/6-31G* combination, the basis for the majority of the AMBER and GAFF biomolecular force fields, does indeed yield molecular dipole moments that are -on average -greater than experimental gas phase dipole moments, but that its predictions have a large variance and likely contain systematic errors with respect to the elements or moieties contained in a given molecule (e.g., species containing sulfur were strongly overpolarized, while pure hydrocarbon species were underpolarized). The use of a larger, more advanced augmented triple-ζ basis set with the HF method substantially improved the consistency of the method, but did not appreciably change the strength of the overpolarization. Used in concert with a PCM model of benzene, the combinations of two relatively simple density functionals (B3LYP and PW6B95) with two different augmented triple-ζ basis sets (aug-cc-pV(T+d)Z and def2-TZVPD) generated consistently overpolarized dipole moments that were -in an average sense -approximately 2 times more overpolarized relative to experimental gas phase data compared to those generated by HF/6-31G*. The use of PCM water increases the overpolarization of these method/basis set combinations even more (to approximately 4 times that of HF/6-31G*). As we will describe in more detail below, we believe that a similar sort of method/basis set combination and the use of implicit (or explicit) solvent -of either moderate dielectric constant or "averaged" between gas phase and high dielectric constant -is strongly justified for charge derivation in future fixed-charge MM force fields, and indeed many practitioners in the force field development community have adopted similar strategies.