While NPA charges remove the problem of orbital overlap through orthogonalization, nevertheless, we find these values are significantly peturbed by the spatial proximity of meta-substituents yielding unrealistic results that correlate poorly with experimental Hammet parameters. In contrast, integration of the electron density over atomic domains, as in the Hirshfeld scheme, avoids problems inherent to basis set based approaches yielding atomic charges that perform well across para-and meta-substitution patterns and which correlate best to observable Hammet parameters. Hirshfeld or other density-based schemes (CM5, Voronoi) are therefore strongly recommended as electronic parameters/descriptors for future physicalorganic or statistical studies, over the widely-used NPA charges. Additionally, where the practitioner has a choice of atom(s)