Evaluation of net atomic charges and atomic and molecular electrostatic moments through topological analysis of the...

The atoms in molecules (AIM) theory may be used to derive atomic charges, atomic volumes and molecular dipole moments from the charge density. The theory is applied to theoretical periodic Hartree-Fock (PHF), density-functional (DFT) and experimental X-ray densities of p-nitroaniline using the program TOPOND and a newly developed program, TOPXD, for topological analysis of densities described by the Coppens-Hansen multipole formalism. Results show that, like dipole moments derived directly from the multipole refinement, AIM-derived atomic and molecular moments are dependent on the multipole model used. As expected, large differences are found between charges derived from the monopole parameters and those from AIM analysis of the experimental model density. Differences between the k'-restricted multipole model (KRMM) and the unrestricted multipole model (UMM) results are preserved in the AIM analysis. The enhancement of the molecular dipole moment of p-nitroaniline in the solid state is confirmed by both experiment and theory but the experimental dipole moment is in much better agreement with theoretical periodic Hartree-Fock and, especially, periodic DFT (PDFT) data when KRMM is used in the refinement. The AIM analysis allows a rigorous definition of the charges of the atoms in molecules and provides a realistic basis for comparison between molecules and between experiment and theory.