Abstract
Charge densities have been determined by the Maximum Entropy Method (MEM) from the high-resolution, low-temperature (T approximately 20 K) 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 (l(max) = 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...O) 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.
Highlights
Inter- and intramolecular hydrogen bonds are important in both molecular and biological chemistry, because they contribute a large part of the interactions responsible for the conformations and functions of many compounds in those fields
Earlier studies have stressed artifacts in Maximum Entropy Method (MEM) densities, which have magnitudes equal to the deformation densities of chemical bonds, and would prohibit the use of the MEM in charge-density studies (Jauch & Palmer, 1993; Jauch, 1994; de Vries et al, 1996; Takata & Sakata, 1996; Roversi et al, 1998). These problems have been overcome by a combination of extensions to the MEM, including the use of a procrystal prior density, the use of static weights in the F constraint, the use of prior-derived F constraints (Palatinus & van Smaalen, 2005) and the definition of a criterion of convergence for the MEM iterations, which is based on difference-Fourier maps (Hofmann, Netzel & van Smaalen, 2007)
Charge densities have been determined by the MEM from Xray diffraction data on six different crystals of amino acids and tripeptides
Summary
Inter- and intramolecular hydrogen bonds are important in both molecular and biological chemistry, because they contribute a large part of the interactions responsible for the conformations and functions of many compounds in those fields. Earlier studies have stressed artifacts in MEM densities, which have magnitudes equal to the deformation densities of chemical bonds, and would prohibit the use of the MEM in charge-density studies (Jauch & Palmer, 1993; Jauch, 1994; de Vries et al, 1996; Takata & Sakata, 1996; Roversi et al, 1998) These problems have been overcome by a combination of extensions to the MEM, including the use of a procrystal prior density (de Vries et al, 1996), the use of static weights in the F constraint (de Vries et al, 1994), the use of prior-derived F constraints (Palatinus & van Smaalen, 2005) and the definition of a criterion of convergence for the MEM iterations, which is based on difference-Fourier maps (Hofmann, Netzel & van Smaalen, 2007). The systematic dependence of properties of hydrogen bonds on the distance between the H atom and acceptor atom is supplemented by an analysis of the properties of covalent bonds with respect to the bond distance
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