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Theoretical study of ionization and one-electron oxidation potentials of N-heterocyclic compounds

Authors

  • Liudmyla K. Sviatenko,

    Corresponding author
    1. Department of Chemistry and Biochemistry, Interdisciplinary Nanotoxicity Center, Jackson State University, Jackson, Mississippi 39217
    2. Kirovohrad Volodymyr Vynnychenko State Pedagogical University, Kirovohrad, 25006, Ukraine
    • Department of Chemistry and Biochemistry, Interdisciplinary Nanotoxicity Center, Jackson State University, Jackson, Mississippi 39217

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  • Leonid Gorb,

    1. Badger Technical Services, Inc., 4815 Bradford Dr, NW Huntsville, Alabama 35805
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  • Frances C. Hill,

    1. US Army ERDC, Vicksburg, Mississippi, 39180
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  • Jerzy Leszczynski

    1. Department of Chemistry and Biochemistry, Interdisciplinary Nanotoxicity Center, Jackson State University, Jackson, Mississippi 39217
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Abstract

A number of density functionals was utilized to predict gas-phase adiabatic ionization potentials (IPs) for nitrogen-rich heterocyclic compounds. Various solvation models were applied to the calculation of difference in free energies of solvation of oxidized and reduced forms of heterocyclic compounds in acetonitrile (AN) for correct reproduction of their standard oxidation potentials. We developed generally applicable protocols that could successfully predict the gas-phase adiabatic ionization potentials of nitrogen-rich heterocyclic compounds and their standard oxidation potentials in AN. This approach is supported by a MPW1K/6-31+G(d) level of theory which uses SMD(UA0) approximation for estimation of solvation energy of neutral molecules and PCM(UA0) model for ionized ones. The mean absolute derivation (MAD) and root mean square error (RMSE) of the current theoretical models for IP are equal to 0.22 V and 0.26, respectively, and for oxidation potentials MAD = 0.13 V and RMSE = 0.17. © 2013 Wiley Periodicals, Inc.

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