Ga. Dilabio et al., Theoretical study of X-H bond energetics (X = C, N, O, S): Application to substituent effects, gas phase acidities, and redox potentials, J PHYS CH A, 103(11), 1999, pp. 1653-1661
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 relevan
t to understanding proton transfer (acid-base), electron transfer (redox),
and H-atom transfer (free radical) reactions. A series of basis set experim
ents has led to an optimum compromise between computational speed and accur
acy. 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 me
thodology to obtain absolute bond dissociation energies for X-H bonds, isod
esmic reaction schemes, substituent effects, redox potentials, and gas-phas
e acid dissociation constants shows the usefulness of this approach.