title: High-level ab initio enthalpies of formation of 2,5-dimethylfuran, 2-methylfuran, and furan.
abstract: A high-level ab initio thermochemical technique, known as the Feller-Petersen-Dixon method, is used to calculate the total atomization energies and hence the enthalpies of formation of 2,5-dimethylfuran, 2-methylfuran, and furan itself as a means of rationalizing significant discrepancies in the literature. In order to avoid extremely large standard coupled cluster theory calculations, the explicitly correlated CCSD(T)-F12b variation was used with basis sets up to cc-pVQZ-F12. After extrapolating to the complete basis set limit and applying corrections for core/valence, scalar relativistic, and higher order effects, the final Δ(f)H° (298.15 K) values, with the available experimental values in parentheses are furan -34.8 ± 3 (-34.7 ± 0.8), 2-methylfuran -80.3 ± 5 (-76.4 ± 1.2), and 2,5-dimethylfuran -124.6 ± 6 (-128.1 ± 1.1) kJ mol(-1). The theoretical results exhibit a compelling internal consistency.
authors.affiliation: Department of Chemistry, Washington State University, Pullman, Washington 99164-4630, United States. dfeller@owt.com
authors.forename: David
authors.initials: D
authors.lastname: Feller
authors.forename: John M
authors.initials: JM
authors.lastname: Simmie
mesh_terms: D005663:Furans / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D005663:Furans; C029060:2-methylfuran; C037555:2,5-dimethylfuran; C039281:furan