Organic Dications: Gas Phase Experiments and Theory in Concert

Knowledge of structure and bonding are integral parts in the understanding of the chemistry of neutral, radicaloid and positively or negatively charged species. The interplay of molecular bonding and the inherent electrostatic repulsion in doubly‐charged molecules expands our insight in the versatility of bonding in electron deficient molecules. Small organic dications are now routinely detected in the gas phase by a variety of mass spectrometric techniques. Ab initio molecular orbital theory has advanced to the stage of accurately predicting potential energy surfaces. This review highlights the symbiotic relationship between gas‐phase ion and computational studies and gives a rationale for the salient bonding features in doubly‐charged organic cations.