Thermochemical properties and group values for nitrogen-containing molecules.
Gas-phase thermochemical group additivity values were derived from CBS-QB3 computational chemistry calculations for 105 noncyclic C/H/O/N molecules. The molecules contain nitrile, nitro, nitroso, nitrite, nitrate, amine, imino, and azo functional groups. The enthalpy of formation, entropy, and heat capacity values for 49 atom-centered groups were derived. The effect of hindered internal rotations was included via rotor potential energy scans and solution of the one-dimensional Schrodinger equation. The average 95% confidence intervals across all derived groups are 1.4 kcal mol(-1) for the enthalpy, 1.3 cal mol(-1) K(-1) for the entropy, and 1.0 cal/mol K for the heat capacity. The presented group values will be useful when employing automatic reaction mechanism generation tools to examine the role of fuel-bound or molecular nitrogen in energy-related or atmospheric processes.
Ashcraft
Robert W
RW
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Green
William H
WH