Analysis of rotational barriers in molecules on the basis of exchange perturbation theory

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Abstract
Exchange perturbation theory of the Rayleigh‐Schrödinger type in first and second orders is applied to a calculation of barriers of internal rotation about single bonds in molecules. The barrier is assumed to arise as a result of exchange interactions between nonbonded atoms; the electrons of these atoms are replaced by one effective electron per atom, with a Gaussian charge distribution. Spins of effective electrons on different atoms are taken to be parallel. The method is applied to a large variety of molecules; calculated results for the barriers are in substantial agreement with experiment. A decomposition of the interaction energy for different conformers and for the barrier itself is given in terms of two‐ and many‐atom exchange interactions.

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