Thermochemical Properties of Polycyclic Aromatic Hydrocarbons (PAH) from G3MP2B3 Calculations
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- 作者：Guillaume Blanquart ; Heinz Pitsch
- 刊名：Journal of Physical Chemistry A
- 出版年：2007
- 出版时间：July 19, 2007
- 年：2007
- 卷：111
- 期：28
- 页码：6510 - 6520
- 全文大小：371K
- 年卷期：v.111,no.28(July 19, 2007)
- ISSN：1520-5215
文摘
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 partof 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 includesall the species usually present in chemical mechanisms for soot formation. Geometric molecular structuresare optimized at the B3LYP/6-31++G(d,p) level of theory. Heat capacity, entropy, and energy content arecalculated from these optimized structures. Corrections for hindered rotor are applied on the basis of torsionalpotentials obtained from second-order M
ller-Plesset perturbation (MP2) and Dunning's consistent basis sets(cc-pVDZ). Enthalpies of formation are calculated using the mixed G3MP2//B3 method. Finally, a groupcorrection is applied to account for systematic errors in the G3MP2//B3 computations. The thermodynamicproperties for all species are available in NASA polynomial form at the following address: http://www.stanford.edu/group/pitsch/.
ller-Plesset perturbation (MP2) and Dunning's consistent basis sets(cc-pVDZ). Enthalpies of formation are calculated using the mixed G3MP2//B3 method. Finally, a groupcorrection is applied to account for systematic errors in the G3MP2//B3 computations. The thermodynamicproperties for all species are available in NASA polynomial form at the following address: http://www.stanford.edu/group/pitsch/.