Electron-density-based calculations of intermolecular energy: case of urea

Kyrill Yu. Suponitsky, Vladimir G. Tsirelson, Dirk Feil, D. Feil

Research output: Contribution to journalArticleAcademicpeer-review

29 Citations (Scopus)

Abstract

The intermolecular interaction energy in crystalline urea has been calculated both from diffraction data and from the Hartree-Fock crystalline electron-density distribution, using a modified atom-atom approximation scheme. The electrostatic part of this energy has been calculated from the atomic multipole moments, obtained by adjustment of the multipole model to experimental X-ray and to theoretical Hartree-Fock structure amplitudes. To obtain the induction energy, multipole moments were calculated from structure amplitudes for the crystalline electron density and from those that refer to the electron density of a superposition of isolated molecules. This worked well for the calculation of the interaction energy from Hartree-Fock data (6% difference from the sublimation-energy value), but not for the interaction energy from experimental data, where the moments of the superposition have to come from Hartree-Fock calculations: the two sets of multipole moments are far too different. The uncertainty of the phases of the structure amplitudes, combined with systematic errors in the theoretical data and noise in the experimental values, may account for the discrepancies. The nature of the different contributions to intermolecular interactions for urea is examined.
Original languageUndefined
Pages (from-to)821-827
Number of pages7
JournalActa crystallographica Section A: Foundations of crystallography
VolumeA55
DOIs
Publication statusPublished - 1999

Keywords

  • METIS-106337
  • IR-59191

Cite this