Predicted Crystal Structures, Analysis, Impact Sensitivities and Morphology of Solid High-Energy Complexes: Alkaline-Earth Carbohydrazide Perchlorates

The crystal structures, density of states, energy gap, thermodynamic properties, impact sensitivities and morphology of beryllium carbohydrazide perchlorate ([Be(CHZ)3](ClO4)2), magnesium carbohydrazide perchlorate ([Mg(CHZ)3](ClO4)2), calcium carbohydrazide perchlorate ([Ca(CHZ)3] (ClO4)2), strontium carbohydrazide perchlorate ([Sr(CHZ)3](ClO4)2) and barium carbohydrazide perchlorate ([Ba(CHZ)3](ClO4)2) were investigated using the density functional theory (DFT) and crystal morphology theory. The results show that all of the complexes have six-coordinated distorted octahedra, which is different from previous works. This was rationalised by consideration of the intermolecular interactions in the crystal structures. Hence the crystal structure is now more reliable. The chemical reactions of the whole molecule may be triggered by an electron transition of CHZ or ClO4 −. Furthermore the energy gaps were observed, and the values of the impact sensitivities were inferred to have the following sequence: [Be(CHZ)3](ClO4)2 > [Mg(CHZ)3](ClO4)2 > [Sr(CHZ)3](ClO4)2 > [Ca(CHZ)3](ClO4)2 > [Ba(CHZ)3](ClO4)2. In addition, the thermodynamic equations at 25-1000 K were obtained. The positive values of the standard molar free enthalpies shows that carbohydrazide perchlorates are stable at 298.15 K. The (1 0 -1) and (0 0 2) faces are the most important growth directions of the crystal morphologies, and have the minimum growth rates. From the cleaved main growth faces, it can be deduced that surface active agents with active hydrogen atoms in the functional groups could be used as crystal-control reagents to control the crystal morphology for alkaline-earth carbohydrazide perchlorates.