A molecular or fragment ion which is made up of the most abundant isotopes of each of its atomic constituents. In the case of compounds that have been artifically isotopically enriched in one or more positions such as $\ce{CH3^{13}CH3}$ or $\ce{CH2D2}$ the principal ion may be defined by treating the heavy isotopes as new atomic species. Thus, in the above two examples, the principal ions would be of masses 31 and 18, respectively.