Please use this identifier to cite or link to this item: http://hdl.handle.net/10316/8242
Title: Absolute Rate Calculations: Atom and Proton Transfers in Hydrogen-Bonded Systems13
Authors: Barroso, Mónica 
Arnaut, Luis G. 
Formosinho, Sebastião J. 
Issue Date: 2005
Citation: ChemPhysChem. 6:2 (2005) 363-371
Abstract: We calculate energy barriers of atom- and proton-transfer reactions in hydrogen-bonded complexes in the gas phase. Our calculations do not involve adjustable parameters and are based on bond-dissociation energies, ionization potentials, electron affinities, bond lengths, and vibration frequencies of the reactive bonds. The calculated barriers are in agreement with experimental data and high-level ab initio calculations. We relate the height of the barrier with the molecular properties of the reactants and complexes. The structure of complexes with strong hydrogen bonds approaches that of the transition state, and substantially reduces the barrier height. We calculate the hydrogen-abstraction rates in H-bonded systems using the transition-state theory with the semiclassical correction for tunneling, and show that they are in excellent agreement with the experimental data. H-bonding leads to an increase in tunneling corrections at room temperature.
URI: http://hdl.handle.net/10316/8242
DOI: 10.1002/cphc.200400285
Rights: openAccess
Appears in Collections:FCTUC Química - Artigos em Revistas Internacionais

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