Anti‐Electrostatic Hydrogen Bonds |
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| Authors: | Prof. Frank Weinhold Dr. Roger A. Klein |
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| Affiliation: | 1. Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison WI 53706 (USA);2. 30 Kimberley Road, Chesterton, Cambridge CB4 1HH (UK) |
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| Abstract: | Ab initio and hybrid density functional techniques were employed to characterize a surprising new class of H‐bonded complexes between ions of like charge. Representative H‐bonded complexes of both anion–anion and cation–cation type exhibit appreciable kinetic stability and the characteristic theoretical, structural, and spectroscopic signatures of hydrogen bonding, despite the powerful opposition of Coulomb electrostatic forces. All such “anti‐electrostatic” H‐bond (AEHB) species confirm the dominance of resonance‐type covalency (“charge transfer”) interactions over the inessential (secondary or opposing) “ionic” or “dipole–dipole” forces that are often presumed to be essential for numerical modeling or conceptual explanation of the H‐bonding phenomenon. |
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| Keywords: | natural bond orbitals bond theory computational chemistry hydrogen bonds resonance |
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