High-level ab initio enthalpies of formation of 2,5-dimethylfuran, 2-methylfuran, and furan

J Phys Chem A. 2012 Nov 29;116(47):11768-75. doi: 10.1021/jp3095984. Epub 2012 Nov 14.

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.

MeSH terms

  • Furans / chemistry*
  • Models, Molecular
  • Molecular Conformation
  • Quantum Theory*
  • Thermodynamics

Substances

  • Furans
  • 2-methylfuran
  • 2,5-dimethylfuran
  • furan