Quantum mechanical and experimental analyses of TNT metabolite 2-hydroxylamino-4,6-dinitrotoluene

Abstract

In this study, a combined quantum mechanical and experimental analyses were performed to investigate crystal structure of the immediate degradation product of TNT, 2-hydroxylamino-4,6-dinitrotoluene (2-HADNT) and to reveal its important chemical properties. Leakage of 2-HADNT has caused serious environmental pollution and therefore raises widespread concerns. In the quantum mechanical analysis, the B3LYP/6-311+G**, B3LYP/aug-c-pVDZ, M06HF/aug-cc-pVDZ, and MP2/aug-cc-pVDZ methods were employed for geometrical optimization and single point calculations of chemical properties of the compound. Such properties include highest unoccupied molecular orbitals (HOMO) – lowest occupied molecular orbitals (LUMO) separation, dipole moment, atomization energy, and vibrational frequencies. Experimental analysis and validation showed that the energy minimized structures acquired from the quantum mechanical analysis were very similar to those obtained by X-ray crystallography. The 6-NO2 groups twist out of plane with respect to the benzene ring in both the crystallographic and energy minimized structures. The 4-NO2 group exhibits co-planarity with the phenyl ring in both the crystallographic and energy minimized structures as well. Unlike TNT, however, the energy barrier to orthogonal conformation is only 3.8kcal/mol. In addition, considerable discrepancies between results obtained from the MP2 and B3LYP methods were observed, which suggest that it has to be very careful when applying B3LYP method to study such class of compounds. Through this study, a more accurate description of the chemical properties of dispersion-dominated aromatic systems was acquired. The chemical properties found from this study can help researchers to better understand the compound of 2-HADNT and to develop effective management plans for such compound so as to minimize its impact on the environment.