E. Bakalbassis, and Alexandra T. Lithoxoidou, Anastasios P. Vafiadis
Sep 16, 2003
Citations
1
Influential Citations
60
Citations
Journal
Journal of Physical Chemistry A
Abstract
DFT/B3LYP is used to calculate the gas-phase absolute and relative phenolic O−H bond dissociation enthalpies (BDEs) in hydroxy/methoxy ortho substituted phenols. The PCM and SCIPCM continuum models are applied to calculate the liquid-phase BDEs. This is the first theoretical determination of liquid-phase BDEs of phenols, the corresponding experimental data of which is rare. The solvated-phase optimized structures of both the parent phenols and their respective radicals are also presented for the first time. A systematic study on a series of 17 different basis sets on phenol, 2-hydroxyphenol (catechol), and 2-methoxyphenol (guaiacol) leads to the optimum 6-31+G(,3pd) basis set. Derived BDEs are among the most accurate of any gas-phase ones (deviations of the absolute gas-phase BDEs do not exceed 0.20 kcal/mol, relative to experiment, and those of the relative ones do not exceed 0.24 kcal/mol). Use of the optimum basis set to obtain the absolute gas-phase BDEs of 2,6-dimethoxyphenol (syringol) and 2,6-dihyd...