A Facile Method for Assessing the Change in Detonation Properties during Chemical Functionalization: The Case of NH₂→NHNO₂ and NH₂→=N⁺=N⁻ Conversions

Abstract

A simple and fast procedure for estimation of the effect of chemical functionalization on the change in detonation properties of energetic materials is reported. The procedure consists of two levels. Computations at Level 1 can be performed with a pocket calculator. At Level 2, quantum-chemical calculations are needed, but these include only three computational tasks: vacuum-isolated molecule relaxation (PBE/DND) → crystal structure prediction (COMPASSII) → crystal cell relaxation (PBE/DND). Thus, we have analyzed transformation of both aromatic and aliphatic amines into the corresponding nitramines and diazo compounds. The calculations at Level 1 indicated that both crystal density (dc) and solid-state enthalpy of formation (ΔHf) are always positive and increase detonation properties, while the calculations at Level 2 revealed the amines that are the most sensitive to such chemical transformation.

Keywords

• nitrogen-rich compound
• energetic material
• density functional theory
• nitramine
• diazo compound