Send to:

Choose Destination
See comment in PubMed Commons below
J Chem Phys. 2008 Oct 28;129(16):164101. doi: 10.1063/1.2997349.

Enthalpy difference between conformations of normal alkanes: Intramolecular basis set superposition error (BSSE) in the case of n-butane and n-hexane.

Author information

  • 1Department of Chemistry and Applied Biosciences, ETH Zurich, 8093 Zurich, Switzerland.


In this paper, an extra error source for high-quality ab initio calculation of conformation equilibrium in normal alkanes-intramolecular basis set superposition error (BSSE)-is discussed. Normal butane (n-butane) and normal hexane (n-hexane) are used as representative examples. Single-point energy difference and BSSE values of trans and gauche conformations for n-butane (and trans-trans-trans and gauche-gauche-gauche conformations for n-hexane) were calculated using popular electron correlation methods: The second-order Moller-Plesset (MP2), the fourth-order Moller-Plesset (MP4), and coupled cluster with single and double substitutions with noniterative triple excitation [CCSD(T)] levels of theory. Extrapolation to the complete basis set is applied. The difference between BSSE-corrected and uncorrected relative energy values ranges from approximately 100 cal/mol (in case of n-butane) to more than 1000 cal/mol (in case of n-hexane). The influence of basis set type (Pople or Dunning) and size [up to 6-311G(3df,3pd) and aug-cc-pVQZ] is discussed.

PubMed Commons home

PubMed Commons

How to join PubMed Commons

    Supplemental Content

    Full text links

    Icon for American Institute of Physics
    Loading ...
    Write to the Help Desk