Abstract
We calculate the standard state entropy, heat capacity, enthalpy, and Gibbs free energy for 13 radicals important for the combustion chemistry of biofuels. These thermochemical quantities are calculated from recently proposed methods for calculating partition functions of complex molecules by taking into account their multiple conformational structures and torsional anharmonicity. The radicals considered in this study are those obtained by hydrogen abstraction from 1-butanol, 2-methyl-1-propanol, and butanal. Electronic structure calculations for all conformers of the radicals were carried out using both density functional theory and explicitly correlated coupled cluster theory with quasipertubative inclusion of connected triple excitations. The heat capacity and entropy results are compared with sparsely available group additivity data, and trends in enthalpy and free energy as a function of radical center are discussed for the isomeric radicals.
| Original language | English (US) |
|---|---|
| Article number | 104314 |
| Journal | Journal of Chemical Physics |
| Volume | 137 |
| Issue number | 10 |
| DOIs | |
| State | Published - Sep 14 2012 |
Bibliographical note
Funding Information:This work was supported in part by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, as part of the Combustion Energy Frontier Research Center under Award No. DE-SC0001198. This work was also supported by the DOE through Grant No. DE-FG02-86ER13579. Part of the computations were performed as part of a Computational Grand Challenge grant at the Molecular Science Computing Facility (MSCF) in the William R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the U.S. Department of Energy's Office of Biological and Environmental Research and located at the Pacific Northwest National Laboratory, operated for the Department of Energy by Battelle.
