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Ultraviolet Absorption Spectra of Substituted Phenols: A Computational Study

Authors

  • Lei Zhang,

    1. Centre for Research in Molecular Modeling and Department of Chemistry and Biochemistry, Concordia University, Montréal, Canada H4B 1R6
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  • Gilles H. Peslherbe,

    Corresponding author
    1. Centre for Research in Molecular Modeling and Department of Chemistry and Biochemistry, Concordia University, Montréal, Canada H4B 1R6
    • To whom correspondence should be addressed: Department of Chemistry and Biochemistry, Concordia University, 7141 Sherbrooke St. West, Montréal, Canada H4B 1R6. Fax: (514) 848-2868; e-mail: ghp@alcor.concordia.ca, muchall@alcor.concordia.ca

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  • Heidi M. Muchall

    Corresponding author
    1. Centre for Research in Molecular Modeling and Department of Chemistry and Biochemistry, Concordia University, Montréal, Canada H4B 1R6
    • To whom correspondence should be addressed: Department of Chemistry and Biochemistry, Concordia University, 7141 Sherbrooke St. West, Montréal, Canada H4B 1R6. Fax: (514) 848-2868; e-mail: ghp@alcor.concordia.ca, muchall@alcor.concordia.ca

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  • This paper is part of a special issue dedicated to Professor J. C. (Tito) Scaiano on the occasion of his 60th birthday.

ABSTRACT

Vertical excitation energies for electronic transitions from the ground state to the first two excited states of phenol, mono- and disubstituted methoxyphenols and methyl-substituted phenols have been characterized with the Time-Dependent Density Functional Theory (TD-DFT), the Complete Active Space Self-Consistent Field method (CASSCF) and the Coupled Cluster with Single and Double Excitations Equation-of-Motion approach (CCSD-EOM) to simulate and interpret experimental ultraviolet absorption spectra. While CASSCF excitation energies for the first two transitions either are grossly overestimated or exhibit a weak correlation with experimental data, both TD-DFT and CCSD-EOM perform very well, reproducing the spectral shifts of both the primary band and secondary band observed upon substitution. The conformational dependence of the calculated excitation energies is generally smaller than the shifts caused by substitution.

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