Hydrogen Bond versus Anti-Hydrogen Bond:  A Comparative Analysis Based on the Electron Density Topology

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 103; no. 32; pp. 6394 - 6401
• Main Authors: Cubero, E, Orozco, M, Hobza, P, Luque, F. J
• Format: Journal Article
• Language: English
• Published: American Chemical Society 12-08-1999
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp990258f

The theory of atoms in molecules is used to examine the nature of anti-hydrogen bond (anti-H bond) interaction. Contrary to what is found in normal hydrogen bond (H bond) complexes, which are characterized by lengthening of the X−H bond and a red shift of its stretching frequency, the anti-H bond leads to a shortening of the X−H bond length and a blue shift of its vibrational frequency. The topological properties of the electron density have been determined for a series of C−H···π complexes, which exhibit either anti-H bond or normal H bond character, as well as for the complexes C6H5F···HCCl3 and C6H6···HF, which are representative cases of anti- and normal H bonds. Inspection of the set of topological criteria utilized to characterize conventional H bonds shows no relevant difference in the two classes of H···π complexes. Analysis of the results suggests that the specific features of the anti-H bond originates from the redistribution of electron density in the C−H bond induced upon complexation, which in turn evidences the different response − dispersion versus electrostatic− of the interacting monomer for stabilizing the complex.