Topological properties of hydrogen bonds and covalent bonds from charge densities obtained by the maximum entropy method (MEM)

Titelangaben

Netzel, Jeanette ; van Smaalen, Sander:
Topological properties of hydrogen bonds and covalent bonds from charge densities obtained by the maximum entropy method (MEM).
In: Acta Crystallographica Section B. Bd. 65 (2009) Heft 5 . - S. 624-638.
ISSN 2052-5206
DOI: https://doi.org/10.1107/S0108768109026767

Volltext

Link zum Volltext (externe URL):

Abstract

Charge densities have been determined by the Maximum Entropy Method (MEM) from the high-resolution, low-temperature (T ≃ 20K) X-ray diffraction data of six different crystals of amino acids and peptides. A comparison of dynamic deformation densities of the MEM with static and dynamic deformation densities of multipole models shows that the MEM may lead to a better description of the electron density in hydrogen bonds in cases where the multipole model has been restricted to isotropic displacement parameters and low-order multipoles (lmax = 1) for the H atoms. Topological properties at bond critical points (BCPs) are found to depend systematically on the bond length, but with different functions for covalent C—-C, C—-N and C—-O bonds, and for hydrogen bonds together with covalent C—-H and N—-H bonds. Similar dependencies are known for AIM properties derived from static multipole densities. The ratio of potential and kinetic energy densities |V(BCP)|/G(BCP) is successfully used for a classification of hydrogen bonds according to their distance d(H⋅sO) between the H atom and the acceptor atom. The classification based on MEM densities coincides with the usual classification of hydrogen bonds as strong, intermediate and weak Jeffrey (1997). {An Introduction to Hydrogen Bonding}. Oxford University Press. MEM and procrystal densities lead to similar values of the densities at the BCPs of hydrogen bonds, but differences are shown to prevail, such that it is found that only the true charge density, represented by MEM densities, the multipole model or some other method can lead to the correct characterization of chemical bonding. Our results do not confirm suggestions in the literature that the promolecule density might be sufficient for a characterization of hydrogen bonds.