First-Principles Prediction of Enthalpies of Formation for Polycyclic Aromatic Hydrocarbons and Derivatives.
In this article, the first-principles prediction of enthalpies of formation is demonstrated for 669 polycyclic aromatic hydrocarbon (PAH) compounds and a number of related functionalized molecules. It is shown that by extrapolating density functional theory calculations to a large basis set limit and then applying a group based correction scheme that good results may be obtained. Specifically, a mean unsigned deviation and root mean squared deviation from the experimental enthalpies of formation data of 5.0 and 6.4 kJ/mol, respectively, are obtained using this scheme. This computational scheme is economical to compute and straightforward to apply, while yielding results of reasonable reliability. The results are also compared for a smaller set of molecules to the predictions given by the G3B3 and G3MP2B3 variants of the Gaussian-3 model chemistry with a mean unsigned deviation and root mean squared deviation from the experimental enthalpies of formation of 4.5 and 4.8 kJ/mol, respectively.
Chemical Science Division, Material Measurement Laboratory, National Institute of Standards and Technology , 100 Bureau Drive, Stop 8320, Gaithersburg, Maryland 20899-8320, United States.
Thomas C
TC
Allison
Chemical Science Division, Material Measurement Laboratory, National Institute of Standards and Technology , 100 Bureau Drive, Stop 8320, Gaithersburg, Maryland 20899-8320, United States.
Donald R
DR
Burgess
D015394:Molecular Structure; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
D011084:Polycyclic Aromatic Hydrocarbons