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Hydrogen Bond at the Dawn of the Xxi Century. New Methods, New Results, New Ideas

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Strength from Weakness: Structural Consequences of Weak Interactions in Molecules, Supermolecules, and Crystals

Part of the book series: NATO Science Series ((NAII,volume 68))

Abstract

Though the hydrogen bond (H-bond) is known since 1920 and in spite of the extraordinary number of books and scientific papers dedicated to it, all attempts to predict its geometry and energetics from the simple knowledge of the chemical structure of the interacting molecules have been so far unsuccessful, a question we have sometimes indicated as the H-bond puzzle. A recent advance in the solution of this problem is represented by the Electrostatic-Covalent H-Bond Model (ECHBM) according to which (/) weak H-bonds are electrostatic in nature but become increasingly covalent with increasing strength, very strong bonds being essentially three-centre-four-electron covalent bonds; (ii) strong and very strong H-bonds may belong only to a limited number of classes which are three for X-H-X homonuclear and four for X-H Yheteronuclear H-bonds; (iii) within each class, H-bonds are the stronger the smaller is ?PA, the difference between the proton affinities of the H-bond donor and acceptor atoms. It is shown that this model leads to an exhaustive classification of all H-bonds in chemical classes which, in turn, becomes a base for the prediction of H-bond strength starting from the chemical structures of the interacting molecules.

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Authors and Affiliations

  1. Department of Chemistry and Centre for Structural Diffractometry, University of Ferrara, 44100, Ferrara, Italy

    Paola Gilli & Gastone Gilli

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  1. Paola Gilli
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  2. Gastone Gilli
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Editors and Affiliations

  1. University of L’Aquila, Italy

    Aldo Domenicano

  2. Budapest University of Technology and Economics, Hungary

    István Hargittai

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Gilli, P., Gilli, G. (2002). Hydrogen Bond at the Dawn of the Xxi Century. New Methods, New Results, New Ideas. In: Domenicano, A., Hargittai, I. (eds) Strength from Weakness: Structural Consequences of Weak Interactions in Molecules, Supermolecules, and Crystals. NATO Science Series, vol 68. Springer, Dordrecht. https://doi.org/10.1007/978-94-010-0546-3_14

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  • DOI: https://doi.org/10.1007/978-94-010-0546-3_14

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  • Print ISBN: 978-1-4020-0710-1

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