We offer a theoretical explanation of the rate processes observed macroscopically in materials composed of aromatic ring structures subjected to high pressure. Earlier workers have made qualitative suggestions that the origin of these processes may be due to interring pi bonding. By making quantum-mechanical calculations on a simple special case of such systems (i.e., two interacting benzene rings), we attempt to produce a quantitative microscopic foundation for the suggestions. We briefly review earlier experimental and theoretical work on the subject and thereby motivate the working hypotheses used in the calculations. The principal hypothesis is that by studying restricted parts of the two benzene-ring energy hypersurface, we can learn something about the pressure-induced rate process for all the arene structures. By use of the modified-neglect-of-diatomic-differential-overlap (MNDO) method and the generalized valence bond ‘‘perfect-pairing’’ (GVP–PP) method supplemented by configuration interaction, we found two metastable ground electronic state dimers of benzene; we suggest that one of these is the source of the observed rate process seen in benzene at high pressure. Further, we suggest that analogous dimerizations are responsible for the rate processes seen in larger arene materials subjected to very high pressures. The detailed geometries and energies of both benzene dimers are given. Suggestions for experimentally testing whether the proposed explanation is correct are given.

Engelke, R., Hay, P. J., Kleier, D. A., & Wadt, W. R. (1983). A theoretical study of possible benzene dimerizations under high-pressure conditions. The Journal of Chemical Physics, 79(9), 4367–4375.