Abstract
The variation with the intermolecular distance of features in hydrogen bond (HB) dimers dependent on the electron density ρ(r) are studied in four complexes representative of weak/medium HB interactions. Topological properties, energy densities and integrated atomic properties are obtained with ρ(r) of dimers at B3LYP/6-311++G(d,p) optimized structures obtained upon fully relaxing the geometry of monomers. The dependence of A–H⋯B bond properties on intermolecular R(H⋯B) distances allows to characterize the nature of the interaction as monomers move nearer from infinite separation. At long distances the interaction is only electrostatic while for separations about 1 Å larger than the equilibrium distance Req, quantum effects arising from ρ(r) begin to dominate. In the immediate neighborhood of Req the interaction is mainly led by the stabilization of the H-donor due in turn to energy lowerings in A and B atoms associated to polarization effects. The mutual penetration of electron densities of donor and acceptor monomers provokes a considerable reduction of atomic volumes for H and B atoms which reveals in the form of redistribution rather than transfer of charge. This range of distances exhibits noncovalent bond features but shortly after, when monomers approximate a few tenths of Å below Req, characteristics typical of covalent interactions begin to appear while the rate of change of all the ρ(r)-dependent properties increases rapidly.
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Dates
| Type | When |
|---|---|
| Created | 23 years, 1 month ago (July 26, 2002, 9:15 a.m.) |
| Deposited | 1 year, 6 months ago (Feb. 10, 2024, 2:25 p.m.) |
| Indexed | 1 month, 4 weeks ago (July 8, 2025, 3:24 a.m.) |
| Issued | 23 years, 8 months ago (Dec. 22, 2001) |
| Published | 23 years, 8 months ago (Dec. 22, 2001) |
| Published Print | 23 years, 8 months ago (Dec. 22, 2001) |
@article{G_lvez_2001, title={Variation with the intermolecular distance of properties dependent on the electron density in hydrogen bond dimers}, volume={115}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1420749}, DOI={10.1063/1.1420749}, number={24}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Gálvez, O. and Gómez, P. C. and Pacios, L. F.}, year={2001}, month=dec, pages={11166–11184} }