Abstract
High-accuracy ab initio thermochemistry is presented for 219 small molecules relevant in combustion chemistry, including many radical, biradical, and triplet species. These values are critical for accurate kinetic modeling. The RQCISD(T)/cc-PV∞QZ//B3LYP/6-311++G(d,p) method was used to compute the electronic energies. A bond additivity correction for this method has been developed to remove systematic errors in the enthalpy calculations, using the Active Thermochemical Tables as reference values. On the basis of comparison with the benchmark data, the 3σ uncertainty in the standard-state heat of formation is 0.9 kcal/mol, or within chemical accuracy. An uncertainty analysis is presented for the entropy and heat capacity. In many cases, the present values are the most accurate and comprehensive numbers available. The present work is compared to several published databases. In some cases, there are large discrepancies and errors in published databases; the present work helps to resolve these problems. © 2012 American Chemical Society.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 9033-9057 |
| Number of pages | 25 |
| Journal | The Journal of Physical Chemistry A |
| Volume | 116 |
| Issue number | 36 |
| DOIs | |
| State | Published - Aug 29 2012 |
| Externally published | Yes |
Bibliographical note
KAUST Repository Item: Exported on 2020-10-01Acknowledged KAUST grant number(s): KUS-I1-010-01
Acknowledgements: This work is supported by Division of Chemical Sciences, Geosciences, and Biosciences, the Office of Basic Energy Science (BES) of the U.S. Department of Energy (DOE) through contract DE-FG02-98ER14914, and by Award No. KUS-I1-010-01, made by King Abdullah University of Science and Technology (KAUST). C.F.G. gratefully acknowledges fellowship support from the National Science Foundation and the Alexander von Humboldt Foundation.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.