The AMBER ff03 force field represents perhaps the first major biomolecular force field application of the more advanced electronic structure methods used in this work . Partial atomic charges for ff03 are obtained by performing a RESP fit to molecular electrostatic potentials calculated using B3LYP/cc-pVTZ and an ε = 4 implicit solvent. Perhaps the main shortcoming to this approach is lack of tight-d and diffuse functions in this basis set, both of which are necessary for obtaining accurate dipole moments. Nonetheless, this work proved to be a forerunner of an approach that has been adopted repeatedly since it was published. For example, the use of DFT methods with triple-ζ basis sets (or their plane-wave equivalent) and ε = 4 implicit solvent has been demonstrated in two recent works regarding training ML models for partial atomic charges and the derivation of partial atomic charges (and Lennard-Jones coefficients) using atoms-in-molecules (AIM) partitioning. In the latter work, the authors argue that ε = 4 implicit solvent is not only a good "average" dielectric environment, but also represents a near ideal dielectric constant for the cancellation of electronic distortion and polarization energies, thereby facilitating comparisons between free energies obtained from fixed-charge MD simulations and experiments. Taking into account the electronic distortion cost was also the motivator for the IPolQ charge derivation method, in which charges are computed by averaging the partial atomic charges obtained from RESP fits performed in gas phase and with explicit water molecules present using the combination of MP2/cc-pV(T+d)Z. As demonstrated in our Results, molecular dipole moments obtained using PCM benzene are likely a reasonable approximation to IPolQ-like approaches (e.g., IPolQ-Mod) that utilize implicit aqueous solvent. It is worth noting, however, that these approaches may underpolarize some molecules by not accurately capturing effects like hydrogen bonding with water that would be captured in the original IPolQ approach utilizing explicit solvent. A possible solution and variant on this idea has recently been proposed by Schauperl et al., who suggest allowing the linear combination of partial atomic charges obtained in gas phase and PCM water to be tuned to reproduce experimental data rather than having the coefficients fixed at ½ as in the IPolQ and IPolQ-Mod models. In addition, this work demonstrates that gas phase molecular ESPs and dipole moments computed using PW6B95/augcc-pV(D+d)Z -a somewhat smaller double-ζ basis set than those used with the DFT methods in the present work -are accurate compared to theoretical reference calculations performed using the method/basis set combination of DSD-PBEP86-D3BJ /aug-cc-pV(Q+d)Z. For the interested reader, we have performed a comparison of the method/basis set combinations used in this work to the same theoretical reference data in our Supporting Information (Figures S6 and ). This comparison largely recapitulates both the qualitative and quantitative trends observed when the comparison is made to gas phase experimental data.