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Theoretical Chemistry Accounts

, Volume 99, Issue 3, pp 166–170 | Cite as

Density functional calculations of the pseudorotational flexibility of tetrahydrofuran

  • Marek Štrajbl
  • Jan Florián
Regular article

Abstract.

The flexibility of the five-membered ring in tetrahydrofuran was investigated using quantum mechanical methods involving density functional, Hartree-Fock, and many-body perturbation theory (MP2, MP4) calculations. We found that motion along the pseudorotational path of tetrahydrofuran is nearly free. The 0.1 kcal/mol energy barrier for pseudorotation, calculated at the highest MP4(SDQ)/6-311++G(2d,p)//MP2/6-311++G(2d,p) level of theory, agrees well with the experimental value of 0.16±0.03 kcal/mol. Similar results were obtained with the S-VWN, B3-LYP and B-LYP density functional calculations using the 6-31G(d) set of atomic orbitals. Also the density functional dipole moments and geometries were in good agreement with both the MP2 and experimental benchmarks. However, all density functional methods that utilized the default integration grid in the Gaussian 94 program were found to provide false stationary points of the C1 symmetry near the pseudorotational angle of 100°. These stationary points disappeared when a denser spherical-product grid was used. Overall, the hybrid B3-LYP functional was found to be the most promising quantum mechanical method for the modeling of biomolecules containing the furanose ring.

Key words: Tetrahydrofuran Pseudorotation Density functional theory Ab initio calculations Conformational analysis 

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Copyright information

© Springer-Verlag Berlin Heidelberg 1998

Authors and Affiliations

  • Marek Štrajbl
    • 1
  • Jan Florián
    • 2
  1. 1.Institute of Physics, Charles University, Ke Karlovu 5, CZ-121 16 Prague 2, Czech RepublicXX
  2. 2.Department of Chemistry, University of Southern California, Los Angeles, CA 90089-1062, USAUS

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