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The Nature of the Hydrogen Bond$
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The Nature of the Hydrogen Bond: Outline of a Comprehensive Hydrogen Bond Theory

Gastone Gilli and Paola Gilli

Print publication date: 2009

Print ISBN-13: 9780199558964

Published to Oxford Scholarship Online: September 2009

DOI: 10.1093/acprof:oso/9780199558964.001.0001

OUTLINE OF A NOVEL TRANSITION-STATE H-BOND THEORY (TSHBT)

Chapter:
(p. 203 ) 6 OUTLINE OF A NOVEL TRANSITION-STATE H-BOND THEORY (TSHBT)
Source:
The Nature of the Hydrogen Bond
Author(s):

Gastone Gilli

Paola Gilli

Publisher:
Oxford University Press
DOI:10.1093/acprof:oso/9780199558964.003.0007

Starting from the concepts of empirical law, model, and scientific theory, a H-bond theory is defined as the encoding of its empirical laws in terms of a more fundamental theory, F. Though both VB and acid-base theories fulfill these condition and give acceptable H-bond theories, a better approach consists in considering the H-bond as a stationary point of a bimolecular reaction pathway leading from D···H-A to D-H···A through the D···H···A transition state. The operator F is now the transition-state theory with its paraphernalia (Leffler-Hammond postulate, Marcus rate-equilibrium theory, linear free-energy relationships, and so on). In this chapter, the validity of this newly-proposed transition-state H-bond theory (TSHBT) is successfully verified on a sample system (the N-H···O/O-H···N competition in the tautomeric ketohydrazone-azoenol system forming intramolecular RAHB) by variable-temperature X-ray crystallography (VTXRC) and Marcus analysis on the DFT-emulated stationary points along the proton-transfer pathway.

Keywords:   H-bond theory, transition-state theory, TSHBT, ketohydrazones, azoenols, intramolecular RAHB, DFT emulation, Marcus analysis, VTXRC

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