Computational methods in organic thermochemistry. 2. Enthalpies and free energies of formation for functional derivatives of organic hydrocarbons.
Standard state enthalpies and free energies of formation for nitrogen-, oxygen-, sulfur-, fluorine-, chlorine-, and silicon-containing compounds can be computed with reasonable accuracy (usually within four and often two kJ/mol) using the G3 and G3MP2 model chemistries. In several of the families, compounds with as many as 10 carbon atoms have been computed. Larger errors are found in the free energies of these longer chain molecules which can be reduced by compensating for the presence of multiple conformers having a significant population at 298.15 K. In some instances, those substances showing large deviations are found to have experimental energies that may be erroneous.
Bond
Douglas
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Computer Chemie Centrum, Friedrich-Alexander-Universität, Erlangen-Nürnberg, Nägelsbach Strasse 25, 91052 Erlangen, Germany. compchemist@ichibond.org