An analysis of the results of ab initio quantum mechanical calculations has been performed on a large number of substituted ethanes, pentanes, hexanes, and dodecanes. The bond critical points of the Atoms in Molecules (AIM) method have been ascertained for these molecules and each is expressed as a FCP, which is defined as the fraction of the bond distance at which the critical point is located. In the ethyl derivatives, the FCPs for the methyl C-H bonds correlate with the charge on the hydrogen atoms. In the longer chain compounds, the FCP for the C-m-C-n bond of charged substituents is related to the difference in inverse distances of the carbon atoms from the charged substituent. An investigation of the amount of s character used in bonds showed that two measures of this quantity, a partial Mulliken overlap population analysis, and a method involving orthogonal Natural Bonding Orbital (NBO) theory orbitals, correlate well with the methylene H-C-H bond angle. In the NBO results for most C-C bonds, the amount of s orbital used in a hybrid orbital is proportional to the amount of the NBO localized hybrid orbital used in the bond. Further analysis shows. that the amount of hybrid orbital used by a carbon atom in a bond to a neighboring carbon atom predicts the FCP; there is a relationship between the topological based method of the atoms in molecules approach and the NBO localization procedure. The s character in bonds is determined by the same inverse distance dependence found for the FCP. A similar result holds for the energies of carbon Is orbitals. Atomic dipole vectors were studied; both their length and direction are influenced by charged substituents. The charged substituent exerts a perturbation on the atomic basin of the carbon atoms in long-chain alkanes that is propagated through space. This distortion determines the values of all investigated parameters.