Bond dissociation energies, electron affinities, and proton affinities are computed for a variety of molecules
containing C−H, N−H, O−H, and S−H bonds using density functional theory with the B3LYP functional.
Thermochemistry in which these bonds are broken or ions are formed is particularly relevant to understanding
proton transfer (acid−base), electron transfer (redox), and H-atom transfer (free radical) reactions. A series
of basis set experiments has led to an optimum compromise between computational speed and accuracy.
Several theoretical models are defined and tested, and the medium and higher-level models approach an
accuracy of 1 kcal/mol. Use of the above methodology to obtain absolute bond dissociation energies for
X−H bonds, isodesmic reaction schemes, substituent effects, redox potentials, and gas-phase acid dissociation
constants shows the usefulness of this approach.
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