title: Structure and electrochemical properties for complexes of nitrocompounds with inorganic ions: A theoretical approach.
abstract: Reduction and oxidation (redox) reactions are widely used for removal of nitrocompounds from contaminated soil and water. Structures and redox properties for complexes of nitrocompounds, such as 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), 2,4-dinitroanisole (DNAN), and 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO), with common inorganic ions (Na(+) , Cl(-) , NO3-) were investigated at the SMD(Pauling)/PCM(Pauling)/MPWB1K/TZVP level of theory. Atoms in molecules (AIM) theory was applied to analyze the topological properties of the bond critical points involved in the interactions between the nitrocompounds and the ions. Topological analyses show that intermolecular interactions of the types O(N)…Na(+) , C-H…Cl(-) ( ONO2-), and C…Cl(-) ( ONO2-) may be discussed as noncovalent closed-shell interactions, while N-H···Cl(-) ( ONO2-) hydrogen bonds are partially covalent in nature. Complexation causes significant decrease of redox activity of the nitrocompounds. Analysis of the reduction potentials of the complexes obtained through application of the Pourbaix diagram of an iron/water system revealed that sodium complexes of NTO might be reduced by metallic iron. © 2016 Wiley Periodicals, Inc.
authors.affiliation: Department of Chemistry and Biochemistry, Interdisciplinary Nanotoxicity Center, Jackson State University, Jackson, Mississippi, 39217.|Department of Organic Chemistry, Oles Honchar Dnipropetrovsk National University, Dnipropetrovsk, Ukraine, 49010.
authors.forename: Liudmyla K
authors.initials: LK
authors.lastname: Sviatenko
authors.affiliation: HX5, LLC, Vicksburg, Mississippi, 39180.
authors.forename: Leonid
authors.initials: L
authors.lastname: Gorb
authors.affiliation: US Army ERDC, Vicksburg, Mississippi, 39180.
authors.forename: Frances C
authors.initials: FC
authors.lastname: Hill
authors.affiliation: Department of Civil and Environmental Engineering, Interdisciplinary Nanotoxicity Center, Jackson State University, Jackson, Mississippi, 39217.
authors.forename: Danuta
authors.initials: D
authors.lastname: Leszczynska
authors.affiliation: Department of Chemistry and Biochemistry, Interdisciplinary Nanotoxicity Center, Jackson State University, Jackson, Mississippi, 39217.
authors.forename: Jerzy
authors.initials: J
authors.lastname: Leszczynski
keywords: AIM theory; DFT method; nitrocompounds; redox potential; solvation energy