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Theoretica chimica acta

, Volume 64, Issue 4, pp 293–311 | Cite as

A molecular orbital study of the rotation about the C-C bond in 1,3-butadiene

  • Charles W. Bock
  • Philip George
  • Mendel Trachtman
Original Investigations

Abstract

The geometry and energy of 1,3-butadiene have been calculated using the 6-311G** basis set as a function of the CCCC dihedral angle-0 ° (trans), 30 °, 60 °, 75 °, 90 °, 120 °, 135 °, 150 °, 165 ° and 180 ° (cis)-assuming that the vinyl groups remain planar. Potential minima are located at 0 ° and 141.4 °, with the trans structure more stable than the gauche by 13.2 kJ mol−1. Potential maxima are located at 76.7 °, giving a barrier height of 25.4 kJ mol−1 relative to the trans structure, and at 180 ° giving a barrier height of 3.0 kJ mol−1 relative to the 141.4 °-gauche structure. Using the 6-31G* basis set the inclusion of electron correlation, accounting for about 52% of the correlation energy, was found to produce no significant change in the shape of the potential energy curve. The magnitude of the expectation energy differences is such that both barriers with respect to the 14l.4 °-gauche maximum structure can be categorized unequivocally as attractive-dominant, whereas the values for the energy barrier with respect to the trans structure, although characteristic of a repulsive-dominant barrier at the 6–311G** level, are sufficiently small that higher level calculations might give the opposite result. Analysis of ΔV nn for the conversion reactions cis → 150 °-gauche, trans → 60 °-gauche, and trans → 90 °-gauche in terms of the individual contributions from the various internuclear interactions shows that nonbonded interactions are important, not only in initiating the destabilization of the crowded cis structure, but also through-out the entire range of CCCC dihedral angles, 0 ° to 180 °.

Key words

1,3-butadiene Rotational barrier 

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Copyright information

© Springer-Verlag 1984

Authors and Affiliations

  • Charles W. Bock
    • 1
  • Philip George
    • 2
  • Mendel Trachtman
    • 3
  1. 1.Chemistry DepartmentPhiladelphia College of Textiles & SciencePhiladelphiaUSA
  2. 2.Biology DepartmentUniversity of PennsylvaniaPhiladelphiaUSA
  3. 3.Chemistry DepartmentPhiladelphia College of Textiles & SciencePhiladelphiaUSA

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