Structure and reactivity of TNT and related species: application of spectroscopic approaches and quantum-chemical approximations toward understanding transformation mechanisms.

This paper presents our latest findings regarding the structure and reactivity of the nitroaromatics, TNT and selected derivatives, within their environmental context. We also demonstrate the useful and proactive role of combined computational chemistry and spectroscopy tools in studying competing transformation mechanisms, particularly those with toxic potential. TNT and selected derivatives were reacted via alkaline hydrolysis as well as via free radical initiators through monochromatic irradiation and through Fenton reactions in complex competing transformation mechanisms.

Application of quantum-chemical approximations to environmental problems: Prediction of physical and chemical properties of TNT and related species.

This paper presents accurate predictions of ecologically important properties of nitroaromatic compounds and their derivatives, including vapor pressure, Henry's law constants, water solubility, octanol/water partition coefficients, heats of formation and ionization potentials. The proposed technique of calculations was based on quantum-chemical methods. The relationship between the chemical structure and mentioned physico-chemical parameters of such widespread military produced contaminants as trinitrotoluene and its derivatives was considered.

Prediction of CL-20 chemical degradation pathways, theoretical and experimental evidence for dependence on competing modes of reaction.

Highest occupied and lowest unoccupied molecular orbital energies, formation energies, bond lengths and FTIR spectra all suggest competing CL-20 degradation mechanisms. This second of two studies investigates recalcitrant, toxic, aromatic CL-20 intermediates that absorb from 370 to 430 nm. Our earlier study (Struct.