title: Theoretical study of ionization and one-electron oxidation potentials of N-heterocyclic compounds.
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.
authors: Department of Chemistry and Biochemistry, Interdisciplinary Nanotoxicity Center, Jackson State University, Jackson, Mississippi 39217, USA.
authors: Liudmyla K
authors: LK
authors: Sviatenko
authors: Leonid
authors: L
authors: Gorb
authors: Frances C
authors: FC
authors: Hill
authors: Jerzy
authors: J
authors: Leszczynski
mesh_terms: D000097:Acetonitriles / Q000737:chemistry; D004583:Electrons; D006571:Heterocyclic Compounds / Q000737:chemistry*; D015394:Molecular Structure; D009574:Nitro Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry
chemical_list: D000097:Acetonitriles; D006571:Heterocyclic Compounds; D009574:Nitro Compounds; D012997:Solvents; C032159:acetonitrile