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Effect of inclusion of electron correlation in MM3 studies of cyclic conjugated compounds
Author(s) -
Tai Julia C.,
Allinger Norman L.
Publication year - 1998
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/(sici)1096-987x(19980415)19:5<475::aid-jcc1>3.0.co;2-j
Subject(s) - delocalized electron , annulene , conformational isomerism , chemistry , conjugated system , electronic correlation , electron delocalization , bond length , molecule , single bond , crystallography , bond order , computational chemistry , organic chemistry , group (periodic table) , polymer
Electron correlation at the Møller–Plesset second‐order level was incorporated into the π‐system portion of MM3 calculations for several conformers of [10]annulene, [18]annulene, bicyclo[5.3.1]undecapentaene, and bicyclo[4.4.1]undecapentaene. The conformers with “localized” C(SINGLE BOND)C π bonds (strongly alternating bond lengths) were found to be of lower energy than their counterparts with “delocalized” C(SINGLE BOND)C π bonds (similar bond lengths) before correlation energy was included. Correlation always lowered the energies of the delocalized conformation more than it did that of the localized conformation, such that often the latter was found to be more stable after correlation energy was included in the calculation. When a delocalized structure was not at a stationary point on the MM3 energy surface, such comparison could not be made. An example is the porphin molecule. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 475–487, 1998