Thermochemical Properties of Polycyclic Aromatic Hydrocarbons (PAH) from G3MP2B3 Calculations

In this article, we present a new database of thermodynamic properties for polycyclic aromatic hydrocarbons
(PAH). These large aromatic species are formed in very rich premixed flames and in diffusion flames as part
of the gas-phase chemistry. PAH are commonly assumed to be the intermediates leading to soot formation.
Therefore, accurate prediction of their thermodynamic properties is required for modeling soot formation.
The present database consists of 46 species ranging from benzene (C6H6) to coronene (C24H12) and includes
all the species usually present in chemical mechanisms for soot formation. Geometric molecular structures
are optimized at the B3LYP/6-31++G(d,p) level of theory. Heat capacity, entropy, and energy content are
calculated from these optimized structures. Corrections for hindered rotor are applied on the basis of torsional
potentials obtained from second-order Møller-Plesset perturbation (MP2) and Dunning's consistent basis sets
(cc-pVDZ). Enthalpies of formation are calculated using the mixed G3MP2//B3 method. Finally, a group
correction is applied to account for systematic errors in the G3MP2//B3 computations. The thermodynamic
properties for all species are available in NASA polynomial form at the following address:  http://www.stanford.edu/group/pitsch/.