A comparative quantum mechanical study of bond separation energies as a measure of cyclic conjugation

Restricted Hartree‐Fock (RHF), second‐order Møller‐Plesset (MP2), and density functional calculations [using the Becke/Lee‐Yang‐Parr (B‐LYP) exchange/correlation gradient‐corrected functionals] employing the 6‐311G(d, p) and 6‐311 + + G(d, p) basis sets have been carried out to calculate isodesmic bond separation energies for reactions involving a number of representative five‐ and six‐membered ring organic compounds. The MP2 and density functional approaches yield reasonably good energies; the density functional method agrees particularly well with experiment, exhibiting a root‐mean‐square error of only 2.5 kcal/mol. Ring geometries are calculated satisfactorily in all approaches but are given particularly accurately by the MP2 approach. A comparison of the B‐LYP bond separation energies with several other definitions of resonance energy shows that these different approaches correlate with each other in a reasonable fashion. © 1995 John Wiley & Sons, Inc.

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