Electron and hole mobilities in polymorphs of benzene and naphthalene: Role of intermolecular interactions

Abstract

The hole and electron mobilities of the polymorphs of benzene and naphthalene crystals are estimated through quantum chemical calculations. The reorganization energy (lambda) and the charge-transfer matrix elements (Hmn) calculated for the two molecules reveal that these crystals can be used for dual applications, for both hole and electron conductance. The electron mobilities are five to eight times more than the hole mobilities for benzene while for naphthalene, the hole mobilities are almost an order magnitude more than the electron mobilities. The transfer matrices for both hole and electron conductance decrease monotonically with increase in the intermolecular distances. Calculations for various unique stacked dimers as determined from the radial distribution functions in both the crystals for the two molecules show strong dependence on the orientations of the rings and for similar intermolecular separations; Hmnhole is larger than Hmnelectron. The crystal mobilities are calculated from the weighted average over all the unique pair of molecules. The overall preference in a crystal for hole or electron mobility depends on the mutual competition of lambdahole/lambdaelectron and Hmnhole/Hmnelectron. From our microscopic understanding of essential parameters, specific dimers are identified from the crystalline solids of the two polymorphs and experimental strategies are suggested to enrich such pairs in aggregates for enhancing mobilities for these organic solids.