Molecular packing in crystals of the aromatic hydrocarbons

Abstract

Abstract The van der Waals energy, quadrupole-quadrupole coupling energy, and hydrogen-hydrogen repulsions have been calculated for the equilibrium structure of crystalline naphthalene and for several displaced structures. The displacements are small rotations of the molecules about their symmetry axes, phased so that the space-group symmetry and unit-cell dimensions are preserved. For structural variations of this type the hydrogen-hydrogen repulsions have a strong minimum within a few degrees angular variation from equilibrium, indicating that these repulsions are dominant and determine the crystal structure for this class of displacement. The attractive van der Waals and quadrupole interactions on the other hand are not minimized at the equilibrium structure; they vary slowly (by a few wavenumbers per degree rotation) and approximately linearly.