1 research outputs found
Database of Small Molecule Thermochemistry for Combustion
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 RQCISDÂ(T)/cc-PV∞QZ//B3LYP/6-311++GÂ(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