Why is Benzene Unique? Screening Magnetic Properties of C6 H6 Isomers.

Abstract

Magnetic properties are commonly used to identify new aromatic molecules because it is generally believed that magnetization and energetic stability are correlated. To verify the potential correlation between the energy and magnetic response properties, we examined a set of 198 isomers of C6 H6 . The energy and magnetic properties of these molecules can be directly compared with no need to invoke any arbitrary reference state because the studied systems are all isomers. Benzene is the global minimum on the potential energy surface of C6 H6 , 35 kcal mol-1 lower in energy than the second most stable isomer, fulvene. Unlike its electronic energy, isotropic magnetizability of benzene is slightly lower than the average magnetizability of its isomers. Altogether, 44 isomers of C6 H6 were identified to have more negative magnetic susceptibility than benzene but were between 67.0 to 168.6 kcal mol-1 higher in energy than benzene. However, benzene is unique in two ways. Analyzing the paramagnetic contribution to the magnetic susceptibility as originally suggested by Bilde and Hansen (Mol. Phys., 1997, 92, 237) revealed that 53 molecules have lower paramagnetic susceptibility than benzene but among monocyclic systems benzene has the least paramagnetic susceptibility. Furthermore, benzene has the largest out-of-plane magnetic susceptibility that originates from the strongest ring current among all studied species.