Dipole moment enhancement in molecular crystals from X-ray diffraction data

作者：Spackman Mark A^*; Munshi Parthapratim; Dittrich Birger

来源：ChemPhysChem, 2007, 8(14): 2051-2063.

DOI：10.1002/cphc.200700339

• ab initio calculations
• charge density analysis
• dipole moment
• electron density
• X-ray diffraction

Although reliable determination of the molecular dipole moment from experimental charge density analyses on molecular crystals is a challenging undertaking, these values are becoming increasingly common experimental results. We collate all known experimental determinations and use this database to identify broad trends in the dipole moment enhancements implied by these measurements as well as outliers for which enhancements are pronounced. Compelling evidence emerges that molecular dipole moments from X-ray diffraction data can provide a wealth of information on the change in the molecular charge distribution that results from crystal formation. Most importantly, these experiments are unrivalled in their potential to provide this information in such detail and deserve to be exploited to a much greater extent. The considerable number of experimental determinations now available has enabled us to pinpoint those studies that merit further attention, either because they point unequivocally to a considerable enhancement in the crystal (of 50% or more), or because the experimental determinations suggest enhancements of 100% or more-much larger than independent theoretical estimates. In both cases further detailed experimental and theoretical studies are indicated.

• 出版日期2007-10-8