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Evaluation of small gaussian basis sets and analysis of substituent effects in monosubstituted benzenes and phenols

Evaluation of small gaussian basis sets and analysis of substituent effects in monosubstituted benzenes and phenols

Journal of the American Chemical Society 107(21): 5856-5863

Ab initio, molecular orbital calculations on a series of monosubstituted benzenes and phenols are reported. These calculations were carried out with minimum basis (MB) sets constructed from small Gaussian atomic basis sets parametrized to mimic the valence shell description of larger basis sets. Total energies, reaction energies, dipole moments, ionization potentials, and charge distributions are presented, and with the help of a statistical analysis the reliability of the calculated results has been assessed and compared with STO-3G and CNDO/2 values. Reactivity indices obtained with these minimum bases are discussed with the help of a linear regression analysis of the highest orbital energy and net .pi. charge distributions with the Taft substituent parameters, .sigma.1 and .sigma.Ro. Finally, the applicability of substituent parameters in ortho-substituted phenols is considered, a unified dual regression equation for the the HOMO orbital energy is derived which includes all para, meta, and ortho isomers, and for the monosubstituted phenols considered in this work it is shown that proximity effects arising between ortho substituents involve primarily .sigma.-electrons.

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Accession: 005401608

Download citation: RISBibTeXText

DOI: 10.1021/ja00307a004

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