Geometries, NMR chemical shifts, atomic charges, and bond orders were calculated at the MP2/6-31G* level of theory for the isopropyl, sec-butyl, tert-butyl, benzenonium, and six methyl- and trifluoromethyl-substituted benzenonium ions. The NPA charges correlate better than the CHELPG, MK, and AIM charges with the experimental and calculated carbon chemical shifts. The electrostatic energies of isomeric ions, calculated by treatment of the NPA charges as point charges, are comparable to their MP2 energy differences. The electrostatic calculations, although classical approximations, provide a qualitative understanding of the coulombic basis of the methyl and trifluoromethyl substituent effects. It is apparent that these species are stabilized by having adjacent, oppositely charged atoms (for example, having the negatively charged carbon of a methyl group bonded to a positive carbon). It is proposed that a methyl group be termed a nucleophilic (rather than electron-donating) substituent and that a trifluoromethyl group be termed an electrophilic substituent. In the benzenonium ions and in toluene, fluoromethylbenzene, difluoromethylbenzene, and benzotrifluoride, the endocyclic angle at the substituent increases with increasing electrophilicity of the substituent. An electrostatic calculation again provides some insight into the coulombic basis of these changes.