Factors Controlling the Barriers to Degenerate Hydrogen Atom Transfers

High-level electronic structure calculations have been used to study the factors contributing to the barriers to degenerate hydrogen-atom transfer (HAT) reactions. Understanding of these reactions is a prerequisite to the development of any more general theory of HAT reactions, and yet, the existing...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2005-04, Vol.127 (16), p.5794-5795
Main Authors: Isborn, Christine, Hrovat, David A, Borden, Weston Thatcher, Mayer, James M, Carpenter, Barry K
Format: Article
Language:English
Subjects:
Ammonia - chemistry
Chemistry
Exact sciences and technology
General and physical chemistry
Hydrofluoric Acid - chemistry
Hydrogen - chemistry
Hydrogen Peroxide - chemistry
Hydroxylamine - chemistry
Kinetics
Methane - chemistry
Models, Molecular
Theory of reactions, general kinetics
Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
Thermodynamics
Water - chemistry
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Summary:High-level electronic structure calculations have been used to study the factors contributing to the barriers to degenerate hydrogen-atom transfer (HAT) reactions. Understanding of these reactions is a prerequisite to the development of any more general theory of HAT reactions, and yet, the existing models for such reactions perform quite poorly when applied to even simple self-exchanges. The reasons behind these failures are elucidated in the present work. They include a near cancellation of bond-strength effects between reactant and transition state, as well as a strong dependence of the geometry of the transition state on the nature of the heavy atoms.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja050024b