The relaxation of molecular crystal structures using a distributed multipole electrostatic model

Abstract

We describe a method for minimizing the lattice energy of molecular crystal structures, using a realistic anisotropic atom–atom model for the intermolecular forces. Molecules are assumed to be rigid, and the structure is described by the center of mass positions and orientational parameters for each molecule in the unit cell, as well as external strain parameters used to optimize the cell geometry. The resulting program uses a distributed multipole description of the electrostatic forces, which consists of sets of atomic multipoles (charge, dipole, quadrupole, etc.) to represent the lone pair, π electron density, and other nonspherical features in the atomic charge distribution. Such ab initio based, electrostatic models are essential for describing the orientation dependence of the intermolecular forces, including hydrogen bonding, between polar molecules. Studies on a range of organic crystals containing hydrogen bonds are used to illustrate the use of this new crystal structure relaxation program, DMAREL, and show that it provides a promising new approach to studying the crystal packing of polar molecules. © 1995 by John Wiley & Sons, Inc.