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Hydrogen bonding in potassium hydrogen carbonate studied by compton scattering on single crystals
Author(s) -
Bräuchler M.,
Lunell S.,
Olovsson I.,
Weyrich W.
Publication year - 1989
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560350623
Subject(s) - chemistry , hydrogen bond , dimer , reciprocal lattice , crystal (programming language) , orthogonalization , molecular physics , compton scattering , scattering , atomic physics , crystallography , molecule , physics , optics , algorithm , computer science , diffraction , programming language , organic chemistry
Compton spectra excited by 241 Am radiation have been measured on thin single‐crystal slices with the scattering vector oriented parallel and perpendicular to the pair of hydrogen bonds in the (HCO 3 ) 2 2−dimers as well as to the plane of the dimers. the reciprocal form factors extracted from the spectra are strongly anisotropic with two extra zero passages in the direction of the hydrogen bonds. the results are in very satisfactory agreement with theoretical data that are calculated for the dimer with and without additional point charges simulating the neighboring ions in the crystal. The calculations have been done with Gaussian basis sets of double‐zeta quality within the Hartree–Fock approximation. The theoretical reciprocal form factors of the monomer HCO 3 −and the dimer show only small differences in the directions perpendicular to the hydrogen bonds, whereas the differences in the hydrogen bond direction are remarkable and account for the experimentally observed features. In comparison to this effect the influence of the neighboring ions by their charges is much smaller, which is even true when taking into account the influence of the neighboring dimers in the crystalline stack in more detail by symmetrical orthogonalization of the combined wave functions. The same orthogonalization procedure applied to a pair of monomers in the spatial arrangement of the dimer yields a reciprocal form factor that in the experimentally reliable range above 1.8 Å accounts for most of the dimerization effect in the direction of the hydrogen bonds. Thus also for this prototype of paired hydrogen bonds (cf., carboxylic acids, DNA, and RNA), it confirms our earlier experimental finding on liquid water now unambiguously, namely that, in the same way as the cohesion in ionic crystals, hydrogen bond formation in bulk matter is distinctly dominated by electrostatic attraction, which is compensated by repulsion owing to the Pauli principle.