KAUST Grant NumberKUS-I1-010-01
Online Publication Date2012-08-29
Print Publication Date2012-09-13
Permanent link to this recordhttp://hdl.handle.net/10754/597918
MetadataShow full item record
AbstractHigh-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.
CitationGoldsmith CF, Magoon GR, Green WH (2012) Database of Small Molecule Thermochemistry for Combustion. The Journal of Physical Chemistry A 116: 9033–9057. Available: http://dx.doi.org/10.1021/jp303819e.
SponsorsThis 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.
PublisherAmerican Chemical Society (ACS)
CollectionsPublications Acknowledging KAUST Support
- Thermochemistry, bond energies, and internal rotor potentials of dimethyl tetraoxide.
- Authors: da Silva G, Bozzelli JW
- Issue date: 2007 Nov 29
- Thermochemical properties and bond dissociation energies of C3-C5 cycloalkyl hydroperoxides and peroxy radicals: cycloalkyl radical + (3)O2 reaction thermochemistry.
- Authors: Auzmendi-Murua I, Bozzelli JW
- Issue date: 2012 Jul 19
- Group additive values for the gas-phase standard enthalpy of formation, entropy and heat capacity of oxygenates.
- Authors: Paraskevas PD, Sabbe MK, Reyniers MF, Papayannakos N, Marin GB
- Issue date: 2013 Nov 25
- Estimating Systematic Error and Uncertainty in Ab Initio Thermochemistry. I. Atomization Energies of Hydrocarbons in the ATOMIC(hc) Protocol.
- Authors: Bakowies D
- Issue date: 2019 Oct 8
- Thermodynamic and ab initio analysis of the controversial enthalpy of formation of formaldehyde.
- Authors: da Silva G, Bozzelli JW, Sebbar N, Bockhorn H
- Issue date: 2006 May 12